Ab initio studies on complexes of ozone with triatomic and larger molecules. 

Ab initio studies on complexes of ozone with triatomic and larger molecules. | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Ab initio studies on complexes of ozone with triatomic and larger molecules. Friedrich Grein This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-2202310/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Using coupled cluster methods with quadruple-zeta basis sets stable structures were found for complexes of ozone with common triatomic molecules as well as with ammonia and methane. The largest dissociation energy of 917 cm − 1 was obtained for the hydrogen bonded O 3 -NH 3 complex, exceeding the value for O 3 -H 2 O (787 cm − 1 ). The high dissociation energy of the O 3 -NH 3 complex is seen as an exception to the expected sequence of stabilities. Large dissociation energies were obtained also for O 3 -SO 2 (717 cm − 1 ), O 3 -N 2 O (688 cm − 1 ), O 3 -HCN (659 cm − 1 ) and O 3 -CO 2 (652 cm − 1 ). Dissociation energies for the C 1 structure (559 cm − 1 ) and C i structure (556 cm − 1 ) of the ozone dimer are nearly identical despite pronounced differences in geometries. Hydrogen bonding of HF, H 2 O, NH 3 and CH 4 with ozone is contrasted to hydrogen bonding with the oxygen molecule. Large shifts in vibrational frequencies were found for the ozone dimer, with a red shift of 51 cm − 1 and a blue shift of 25 cm − 1 for the antisymmetric stretching band of ozone. Larger frequency shifts are also seen for complexes of ozone with NH 3 , HCN, H 2 O and N 2 O. O3-H2O O3-H2S O3-HCN O3-NH3 O3-CH4 O3-CO2 O3-O3 O3-SO2 O3-N2O O3-NO2 complexes Coupled cluster calculations Structures and dissociation energies Vibrational frequencies Hydrogen bonding Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 Introduction Following a recent study on complexes of ozone with diatomic molecules [1], in the present paper complexes of ozone with the triatomic molecules H 2 O, H 2 S, HCN, CO 2 , O 3 , SO 2 , N 2 O, NO 2 , as well as with NH 3 and CH 4 , are to be investigated. All these molecules are present in the atmosphere. Most of them, in particular O 3 , CO 2 , SO 2 , NO 2 , N 2 O, NH 3 and CH 4 , are considered to be air pollutants, causing problems to human health and plant life. They are also related to climate change. Ozone it is a powerful oxidizer in reacting with other surrounding molecules. Complexes with ozone are often the first step in forthcoming chemical reactions. Several of the systems covered here have received prior attention in the literature. In particular, the O 3 -H 2 O complex was studied early on due to its significance in atmospheric reactions, with experimental and theoretical studies being available. The aim of this work is the search for the most stable isomers of each system. While in principle large multidimensional potential surfaces would be required for each complex, such is not practical when properties of many systems – in the present case many complexes with ozone - are to be compared and to be contrasted. Hydrogen bonding (or potentially hydrogen bonding) is involved in complexes of ozone with H 2 O, H 2 S, HCN, NH 3 and CH 4 , and “oxygen bonding” is seen in complexes with O 3 , CO 2 , SO 2 , NO 2 and N 2 O. The study of a large number of ozone complexes at a high level of theory will allow for interesting and important comparisons to be made. Computational Methods And Symmetry Considerations Coupled cluster singles, doubles and perturbative triples CCSD(T) methods [2, 3] were used, with augmented correlation consistent aug-cc-pVXZ (AVXZ) basis sets [4, 5]. All geometry optimizations were performed with the AVQZ basis set, keeping in most cases the geometry of the monomers held fixed at their respective optimized monomer values. Dissociation energies were corrected for the basis set superposition error (BSSE), as calculated by the method of Boys and Bernardi [6]. In several cases extrapolations to the complete basis set (CBS) limit were performed. They are based on the exponential method proposed by Halkier et al. [7], using CCSD(T)/AVXZ energies with X = D, T, Q. Harmonic vibrational frequencies were obtained by the CCSD(T)/AVDZ method, having all geometry parameters optimized. Calculations are performed using the Gaussian 16 [8] computer programs. Many of the complexes have C s symmetry. There are two planes of symmetry to be considered. One, named Cs-A, is the plane of the ozone molecule, whereas the other, named Cs-B, is the plane perpendicular to the plane of ozone. In the Cs-A case, the other monomer can be in cis (Cs-A-cis) or trans (Cs-A-trans) orientation relative to O 3 . Another possibility is atom A of an AB 2 molecule to be located in the plane of ozone whereas the two B atoms are positioned above and below this plane, such as to retain C s symmetry (Cs-A ppd). For complexes with Cs-B symmetry, the other monomer may lie in the Cs-B plane (Cs-B inpl), or for AB 2 molecules be oriented perpendicular to this plane (Cs-B ppd). Structures And Dissociation Energies For Complexes Of Ozone With Ho, Hs, Hcn, Nh And Ch In Table 1 CCSD(T)/AVQZ calculated dissociation energies are given for complexes of ozone with the hydrides H 2 O, H 2 S, HCN, NH 3 and CH 4 . Table 1 Dissociation energies D e (cm − 1 ) for complexes of ozone with H 2 O, H 2 S, HCN, NH 3 and CH 4 . BSSE corrected CCSD(T)/AVQZ results. System Symmetry D e O 3 - H 2 O C 1 787.2 O 3 -H 2 O Cs-B ppd 765.1 O 3 -H 2 O Cs-B inpl 736.6 O 3 -H 2 O Cs-A trans 681.4 O 3 -H 2 O Cs-A cis 680.3 O 3 - H 2 S C 1 629.0 O 3 -H 2 S Cs-B ppd 609.1 O 3 -H 2 S Cs-A cis 440.0 O 3 -H 2 S Cs-B inpl 390.7 O 3 -H 2 S Cs-A trans 350.8 O 3 - HCN NCH-Cs-B inpl 659.0 O 3 -HCN C 1 632.8 O 3 -HCN C 2v 625.4 O 3 - NH 3 Cs-B O 3 :HNH 2 917.5 O 3 -NH 3 Cs-B O 3 :H3N 209.3 O 3 - CH 4 Cs-B HCH 3 :O 3 352.6 O 3 -CH 4 Cs-B H 3 CH:O 3 320.3 O 3 -H 2 O complex Complexes of ozone with water received much attention in the literature. Microwave [9] and infrared spectroscopy [10] studies were performed early on. For a review up to 2005 see Sennikov et al. [11]. There are also several theoretical treatments. The most recent ones are by Anglada et al. [12], Kumar and Sathyamurthy [13], Wang et al. [14] and Hui and Lemke [15]. In the present work, in agreement with literature results, a C 1 conformer (Fig. 1 ) is found to be most stable, having D e =787 cm − 1 . The Cs-B ppd structure (Fig. 2 ) with a D e of 765 cm − 1 , and the Cs-B inplane structure (Fig. 3 ) with D e =737 cm − 1 have dissociation energies close to the value for C 1 . Cs-B inplane represents a transition state for H 2 O in C 1 symmetry to move through the Cs-B plane from one side to the other. This is likely the C s structure proposed by microwave studies [9]. For the fully planar Cs-A cis and the Cs-A trans structures D e values of 680 and 681 cm − 1 , respectively, were obtained. The Cs-A cis structure corresponds to a transition state for the C 1 conformer to move from above to below the O 3 plane. Comparisons of calculated dissociation energies with values obtained by Anglada et al. [12], using the CCSD(T)/CBS//QCISD/AVTZ method, by Kumar and Sathyamurthy [13], using the CCSD(T)/AVQZ //CCSD(T)/AVTZ method, and by Hui and Lemke [15], using the CCSD(T)/AVQZ method with CBS (DTQ), are shown in Table 2 . Most results are within 50 cm − 1 of the present ones. Table 2 Comparison of calculated dissociation energies D e (in cm − 1 ) for O 3 -H 2 O complexes with literature values. Structure Present Anglada et al. [12] Kumar et al. [13] Hui et al. [15] C 1 787 836 (A4) 762 (leg) 804 Cs-B ppd 765 794 (A5) 766 (eclips) --- Cs-B inpl 737 --- 734 (dipole) --- Cs-A trans 681 717 (A3) 637 (trans) 616 Cs-A cis 680 703 (A1) 682 (cis) 612 O 3 -H 2 S complex Complexes of ozone with hydrogen sulfide H 2 S have structures and energetic relationships very similar to O 3 -H 2 O complexes. Dissociation energies for O 3 -H 2 S complexes are about 150 to 300 cm − 1 lower than for O 3 -H 2 O. Most stable is a C 1 structure (Fig. 4 ), close in geometry to C 1 of O 3 -H 2 O (with D e of 629 cm − 1 vs. 787 cm − 1 for O 3 -H 2 O), followed by the Cs-B ppd structure (609 cm − 1 vs 711 cm − 1 for O 3 -H 2 O). Dissociation energies for the cis and trans structures are 440 and 351 cm − 1 , respectively, again 200 to 300 cm − 1 lower than for O 3 -H 2 O. Vahedpour et al. [16] studied the atmospheric reaction of O 3 with H 2 S, showing by B3LYP/6-311 + + G(3df,3pd) calculations that O 3 + H 2 S forms a stable complex. Starting from this complex, over a series of intermediate products, H 2 O + SO 2 is obtained. The BSSE corrected dissociation energy for the O 3 -H 2 S complex is given as 482 cm − 1 , having a geometry close to the C 1 geometry obtained here. O 3 -HCN complex Mielke and Andrews [17] performed infrared studies on the O 3 -HCN complex observing a number of new bands. The complex was assumed to have C 2v symmetry. Using the CCSD(T) method the Cs-B inplane structure with N closest to O 3 (Fig. 5 ) is most stable (659 cm − 1 ). This is followed by the C 1 (633 cm − 1 ) and C 2v (625 cm − 1 , Fig. 6 ) conformers having hydrogen closest to O 3 . Despite large differences in geometry, all three structures are calculated to have similar dissociation energies. In a theoretical study on C-H···O hydrogen bonded complexes, Turi and Dannenberg [18] performed calculations on the O 3 -HCN complex. Using the MP2/D95++(d,p) method they obtained a counterpoise corrected dissociation energy of 1.76 kcal/mol (616 cm − 1 ) for the C 2v structure. O 3 -NH 3 complex Many different structure s of the O 3 -NH 3 complex were investigated. The by far most stable structure has O 3 facing NH 3 in Cs-B symmetry, with NH 3 tilted such that one hydrogen points towards O 3 (Cs-B O 3 :HNH 2 , Fig. 7 ). It has a large dissociation energy of 917 cm − 1 and no imaginary frequencies. All other structurers considered are much less stable. For example, the one with O 3 facing the three hydrogens of NH 3 , also having C s symmetry (Cs-B O 3 :H 3 N), has D e =209 cm − 1 . According to calculated vibrational frequencies, it is not stable. Structures with N of NH 3 facing the central oxygen of ozone (O 3 turned away), as well as a “hydrogen bonded” structure with N-H-O-O-O in the same plane, have very low dissociation energies. Lucchese et al. [19] performed SCF calculations with a minimal basis set on the NH 3 -O 3 and NH 3 -SO 2 complexes. For the NH 3 -O 3 complex with a simplified geometry (O 3 facing N of NH 3 but not tilted, O3:NH3) they obtained a dissociation energy of 2.24 kcal/mol, or 783 cm − 1 . Asgharzade and Vahedpour [20] reported B3LYP results for tropospheric oxidation reactions, including the NH 3 + O 3 reaction. Starting from the most stable O 3 -NH 3 complex leads in a series of steps to HO 2 + H 2 NO, but starting from the O 3 -H 3 N complex leads to HO 2 + NO + H 2 . Their CCSD(T)//B3LYP/6-311 + + G (3df, 3pd) results are 1.41 kcal/mol (493 cm − 1 ) for the O3:NH3 complex (again not tilted), and 0.57 kcal/mol (199 cm − 1 ) for the O 3 :H 3 N complex. O 3 -CH 4 complex The most stable structure of the O 3 -CH 4 complex has Cs-B symmetry, with O 3 facing three hydrogens of CH 4 (Cs-B CH3-O3, D e =353 cm − 1 , Fig. 8 ). O-CH2 is located in the Cs-B plane, with the other oxygens and hydrogens lying above and below this plane. Another structure, with O 3 facing two hydrogens of CH 4 , also in Cs-B symmetry, has D e =320 cm − 1 . Walker et al [21] performed Fourier-transform microwave studies on the O 3 -CH 4 complex. They found the complex to have a plane of symmetry, corresponding to the C s plane found here. They reported the shortest C-O distance to be 3.57 Å, compared to 3.24 Å calculated here for the most stable structure. Structures and dissociation energies for complexes of ozone with CO 2 , O 3 , SO 2 , N 2 O, NO 2 In Table 3 CCSD(T)/AVQZ calculated dissociation energies are given for complexes of ozone with CO 2 , O 3 , SO 2 , N 2 O and NO 2 . Table 3 Dissociation energies D e (cm − 1 ) for complexes of ozone with CO 2 , O 3 , SO 2 , N 2 O and NO 2 . BSSE corrected CCSD(T)/AVQZ results. System Symm/Struct. D e -CCSD(T) O 3 -CO 2 C 2v 651.7 a O 3 -CO 2 Cs-A trans 467.6 O 3 -CO 2 Cs-A cis 394.7 O 3 - O 3 C 1 559.1 O 3 -O 3 C i 556.2 O 3 -O 3 Cs-B inpl 500.1 O 3 -O 3 Cs-A ppd 462.2 O 3 - SO 2 C 1 716.9 O 3 -SO 2 Cs-A ppd 636.6 O 3 -SO 2 Cs-B inpl 513.6 O 3 -SO 2 Cs-B ppd 510.0 O 3 - N 2 O Cs-B inpl-O 688.0 O 3 -N 2 O Cs-B inpl-N1 560.1 O 3 -N 2 O Cs-B inpl-N2 242.5 O 3 - NO 2 Cs-A ppd 496.9 a. CBS value is 676.9 cm − 1 O 3 -CO 2 complex The most stable O 3 -CO 2 complex has a C 2v structure (Fig. 9 ) with a dissociation energy of 652 cm − 1 . At all levels of basis set but before BSSE corrections, a Cs-B inpl structure has a slightly lower energy (only 4 cm − 1 ) than the C 2v structure. However, due to its lower BSSE value, the C 2v isomer becomes more stable after BSSE correction. Fully planar structures are Cs-A cis with D e =395 cm − 1 , and Cs-A trans with D e =468 cm − 1 . Cs-A cis has a quadrupolar alignment, with CO 2 shifted nearly parallel relative to O 3 . The dissociation energy for the C 2v conformer extrapolated to the complete basis set is 677 cm − 1 , compared to the BSSE adjusted CCSD(T) value of 652 cm − 1 . Seif et al. [22] obtained BSSE corrected dissociation energies of 6.87 kJ/mol or 574 cm − 1 for the C 2v (or Cs-B inplane, not clear) structure and 4.40 kJ/mol or 368 cm − 1 for the Cs-A trans structure, using the MP2/AVDZ method. For the most stable (planar) structure of the CO 2 complex with the oxygen molecule a dissociation energy of 230 cm − 1 was found [23]. O 3 -O 3 complex From CCSD(T)/AVDZ potential energy surfaces, Azofra et al. [24] found five stable minima for the ozone dimer, having CCSD(T)/AVTZ dissociation energies of 2.24 kcal/mol (783 cm − 1 ) for the C i structure, 1.89 kcal/mol (661 cm − 1 ) for the Cs-B inplane structure, and much lower dissociation energies for the remaining structures. Gadzhiev et al. [25] studied the oxygen allotropes O n (n ≤ 6), including the O 3 -O 3 complex. Calculated CCSD(T)/cc-pCVTZ (C for additional core orbitals) dissociation energies are 8.3 kJ/mol or 694 cm − 1 for the C i structure, and 7.3 kJ/mol or 610 cm − 1 for the Cs-B inplane structure. Studying homo- and heterodimers of sulphur dioxide and ozone Ford [26] obtained a BSSE corrected dissociation energy of 11.21 kJ/mol or 937 cm-1 for the C i structure of the ozone dimer, using the MP2/AVTZ method. In the present investigation, the C i structure and other structures were investigated for singlet O 3 -O 3 . By the CCSD(T)/AVQZ method a BSSE corrected dissociation energy of 556 cm − 1 was obtained for the C i isomer (Fig. 10 ). However, due to one imaginary frequency found for this structure (by both MP2 and CCSD(T) methods, using various basis sets) a C 1 structure (Fig. 11 ) was also investigated, having relaxed symmetry constraints. Its CCSD(T)/AVQZ BSSE corrected dissociation energy is almost the same, 559 cm − 1 . CCSD(T) results for C i and C 1 structures using AVDZ to AVQZ basis sets are shown in Table 4 . Before BSSE corrections, the C 1 structures are much more stable than their C i counterparts. For both structures D e and BSSE values decrease as the basis set is increased. For each basis set, D e and BSSE values are higher for C 1 than for C i , due to shorter interatomic distances in C 1 . However, with BSSE values decreasing faster than D e values, the BSSE corrected dissociation energies increase rather than decrease. For AVDZ and AVTZ the C 1 values are markedly higher than the C i values. At the highest level of basis set, however, the BSSE corrected D e values for C i and C 1 are about the same, 556 and 559 cm − 1 , respectively. Table 4 Calculated dissociation energies D e (cm − 1 ) for the C i and C 1 structures of O 3 -O 3 before and after BSSE correction. Method C i C 1 D e BSSE D e -BSSE D e BSSE D e -BSSE CCSD(T)/AVDZ 733.8 324.4 409.4 819.3 373.5 445.8 CCSD(T)/AVTZ 661.9 167.8 494.1 782.3 216.6 555.7 CCSD(T)/AVQZ 593.3 37.1 556.2 651.8 92.7 559.1 On account of the nearly equal dissociation energies of the C i (Fig. 10 ) and C 1 (Fig. 11 ) conformers as obtained by the CCSD(T) method, a decision on which is the leading structure cannot be made. CBS values calculated by the exponential method are 533 cm − 1 for C i and 516 cm − 1 for C 1 , favoring the C i structure as being more stable. The C 1 structure has a quadrupolar arrangement, with the two ozone molecules shifted parallel relative to each other, allowing for shorter O-O distances (see later). In addition to the C 1 and C i structures, results were obtained for the Cs-B inplane (500 cm − 1 ) and Cs-A ppd (462 cm − 1 , Fig. 12 ) structures. Dissociation energies for the C i and Cs-B inplane structures obtained by Azofra et al. [24] and Gadziev et al. [25] are much larger than found here. It appears that in both cases BSSE corrections were not applied. O 3 -SO 2 complex Sulfur dioxide, SO 2 , is released into the atmosphere when sulfur containing fuels are burned. The structures of the O 3 -SO 2 complex are quite similar to those of the ozone dimer. Most stable is a C 1 structure (Fig. 13 ) with a dissociation energy of 717 cm − 1 . This is followed by the Cs-A ppd conformer with 637 cm − 1 (Fig. 14 ) and by Cs-B inpl (514 cm − 1 ). The Cs-B ppd structure corresponds to the C i structure of the ozone dimer. It has a D e of 510 cm − 1 . Cs-A cis and trans structures are much less stable. Using the MP2/AVTZ method Ford [27] obtained a BSSE corrected value of 12.18 kJ/mol or 1018 cm − 1 for the C 1 structure. Azofra and Scheiner [27] performed CCSD(T)/AVTZ calculations on dimers, trimers and tetramers of SO 2 with CO 2 . The SO 2 dimer (corresponding to the O 3 dimer) was found to have a large dissociation energy of 1056 cm − 1 . O 3 -N 2 O complex The O 3 -N 2 O complex is of interest, as nitrous oxide may be one of the most ozone depleting substances in the atmosphere [28]. Three structures of the O 3 -N 2 O complex were found to be stable. All have C s symmetry. They belong to the Cs-B inplane category, with N 2 O lying in the plane perpendicular to the plane of ozone. The differences consist in either the oxygen (Cs-B inpl-O, D e =688 cm − 1 ), the terminal nitrogen (Cs-B inpl-N1, D e =560 cm − 1 ) or the central nitrogen (Cs-B inpl-N2, D e =243 cm − 1 ) of N 2 O being closest to the central oxygen of ozone. The structure with the oxygen of N 2 O closest to ozone (Fig. 15 ) has the highest dissociation energy. Cis and trans structures with N 2 O lying in the plane of ozone have dissociation energies in the range of 200 cm − 1 . Several structures in C 1 symmetry were also considered. They optimized to close lying C s structures. No literature could be found on the O 3 -N 2 O complex. The N 2 O complex with O 2 was discussed by Salmon and Lane [29]. Its structure was found to be planar slipped parallel, having a CCSD(T)-F12b/AVQZ dissociation energy of 280 cm − 1 . O 3 -NO 2 complex NO 2 , nitrogen dioxide, is formed when fossil fuels are burned, and is released into the atmosphere, where it constitutes one of the major air pollutants. Calculations on many different structures of the O 3 -NO 2 complex were attempted. However, only in one case could geometry optimizations be completed. This structure, with D e =497 cm − 1 , has Cs-A ppd symmetry, with N lying in the plane of ozone, and the O’s of NO 2 lying above and below this plane (Fig. 16 ). It is possible that other structures of the O 3 -NO 2 complex have lower energies. Such is indicated by the structure found having one imaginary frequency. Harmonic Vibrational Frequencies In Table 5 harmonic vibrational frequencies are given for ozone complexes in their most stable structures. Table 5 Harmonic vibrational frequencies (cm − 1 ) and frequency shifts (cm − 1 ) for most stable O 3 -ABC complexes. CCSD(T)/AVDZ results. a Complex Symmetry Ozone frequencies b ABC frequencies b O 3 -H 2 O C 1 709 + 1 973 + 2 1118 + 1 1636 -2 3779 -9 3895 -10 O 3 -H 2 S C 1 706 -2 968 -3 1116 -1 1187 -2 2693 + 1 2714 + 1 O 3 -HCN Cs-B inpl 706 -2 981 + 10 1121 + 4 698 + 5 c 2083 + 6 3417 + 1 O 3 -HCN C2v 707 -1 971 0 1116 -1 727 +34 769 + 76 2077 0 3395 -21 O 3 -NH 3 Cs-B O3:HNH2 708 0 979 + 8 1121 + 4 1083 + 12 1648 -2 3432 -3 O 3 -CH 4 Cs-B HCH3:O3 704 -4 965 -6 1115 -2 1321 + 2 1537 + 3 3041 -3 O 3 -CO 2 Cs-B inpl 714 +6 968 -3 1117 0 656 -3 1317 +1 2341 +1 O 3 -O 3 C 1 703 -5 927 − 44 1115 -2 704 -4 991 + 20 1115 -2 O 3 -O 3 C i 705 -3 920 − 51 1114 -3 706 -2 996 + 25 1116 -1 O 3 -O 3 Cs-B inpl 704 -4 971 0 1116 -1 705 -3 972 + 1 1117 0 O 3 -SO 2 C 1 708 0 969 -2 1117 0 476 + 1 1051 + 4 1213 + 1 O 3 -N 2 O Cs-B inpl-O 703 -5 973 + 2 1116 -1 563 -4 1282 + 5 2249 + 8 a. For NH 3 and CH 4 only frequencies with the largest changes are given. b. Shown are frequencies calculated for the complex and their differences from frequencies of the isolated monomers, + for blue shifts, - for red shifts. The ozone frequencies are 708 cm -1 (A 1 ), 971 cm -1 (B 2 ) and 1117 cm -1 (A 1 ). c. Same result for the other component. Fairly large frequency shifts were found for the ozone dimer. In the C i complex the ozone B 2 band (971 cm − 1 as calculated) is split into frequencies of 920 (-51) and 996 (+ 25) cm − 1 . Similar results were obtained for the C 1 isomer of this complex (shifts of -44 and + 20 cm − 1 ). Frequency shifts for the C i complex calculated by the higher level CCSD(T)/AVTZ method are nearly the same (-47, + 21 cm − 1 for the B 2 mode). Infrared studies of the ozone dimer in an argon matrix performed by Bahou et al. [30] found a small blue shift (2 cm − 1 ) as well as a small red shift (3 cm − 1 ) for the B 2 band. It is assumed that the conformer observed in the argon matrix was not the C i or C 1 conformer but Cs-B inpl instead, for which only small frequency shifts were found (Table 5 ). Azofra et al. [24] obtained red shifts only for all five O 3 -O 3 structures investigated. For the C i dimer shifts of -10 cm − 1 for the A 1 , -32 cm − 1 for the A 1 and − 111 cm − 1 for the B 2 mode were obtained. Gadzhiev et al. [25] calculated frequency shifts of -34 and + 18 cm − 1 for the C i dimer, and + 2, +4 cm − 1 for Cs-B inpl . Frequency shifts are small for the most stable isomer of O 3 -HCN (Cs-B inpl). However, they are quite large for the C 2v complex, with shifts of + 34 and + 76 cm − 1 for the degenerate bending motion at 693 cm − 1 , and − 21 cm − 1 for the asymmetric stretch at 3416 cm 1 . Mielke and Andrews [17] observed a shift of -30 cm − 1 for the asymmetric stretch at 3303.8 cm − 1 , assuming the complex had C 2v symmetry (compared to -21 cm − 1 calculated). Only small frequency shifts were calculated for the C 1 structure of the O 3 -SO 2 complex, with a blue shift of 4 cm − 1 for one of the SO 2 bands. For the O 3 -NH 3 complex blue shifts of 8 cm − 1 (for the B 2 band of ozone) and 12 cm − 1 (for the lowest NH 3 bands, N-H wagging) were found. Large blue shifts of 10 and 4 cm − 1 for the ozone bands, and 5 and 6 cm − 1 for HCN are seen for the O 3 -HCN complex. Large red shifts of 9 and 10 cm − 1 of the H 2 O bands and small blue shifts (1 and 2 cm − 1 ) of the ozone bands were calculated for the C 1 structure of the O 3 -H 2 O complex. By infrared spectroscopy Schriver et al. [10] observed blue shifts of about 5 cm − 1 for the three ozone bands of the O 3 -H 2 O complex. For the C 1 structure blue shifts of 3 to 6 cm − 1 were found for the ozone frequencies, and red shifts of -6 and − 7 cm − 1 for the stretching frequencies of H 2 O. Kumar and Sathyamurthy [13] gave detailed vibrational frequencies and frequency shifts for the O 3 -H 2 O complexes, calculated at the CCSD/AVTZ level of theory. Contrary to larger frequency shifts for the O 3 -H 2 O complex, only small ones, up to 3 cm − 1 , were obtained for the O 3 -H 2 S complex. For O 3 -N 2 O the lowest O 3 frequency is red shifted by 5 cm − 1 , whereas the NO 2 frequencies are red (5 cm − 1 ) and blue (5 and 8 cm − 1 ) shifted. Discussion In Table 6 , dissociation energies and shortest interatomic distances are listed for the most stable isomers of complexes with ozone. Table 6 Dissociation energies D e (cm − 1 ) and shortest interatomic distances (Å) of the most stable isomers of complexes with ozone. a Complex Fig. Structure D e Shortest distances O 3 -NH 3 7 Cs-B O 3 :HNH 2 917 O6-H2 2.71, O7-H2 2.71, O6-N1 2.91 O 3 -H 2 O 1 C 1 (A4) 787 O3-H6 2.46, O2-H6 2.75, O1-H6 2.87 O 3 -SO 2 13 C 1 717 O2-O6 2.99, O2-S4 3.06, O3-O6 3.11 O 3 -N 2 O 15 Cs-B inpl-O 688 O2-O6 2.94, O3-O6 2.94, O2-N4 3.04 O 3 -HCN 5 NCH-Cs-B inpl 659 O1-N4 3.09, O2-N4 3.18, O3-N4 3.18 O 3 -CO 2 9 C 2v 652 O2-C4 3.02, O3-C4 3.02, O2-O5 3.23 O 3 -H 2 S 4 C 1 (A4) 629 O3-H5 2.84, O2-H5 2.84, O1-H5 3.12 O 3 -HCN 6 C 2v 625 O2-H4 2.57, O3-H4 2.57, O1-H4 3.02 O 3 -O 3 C 1 11 C 1 559 O2-O4 2.75, O3-O6 2.88, O3-O4 3.04 O 3 -O 3 C i 10 C i 556 O2-O6 2.93, O3-O5 2.93, O1-O6 3.54 O 3 -CH 4 8 Cs-B HCH3:O 3 353 O7-H5 2.84 O8-H5 2.84, O6-H5 2.94 O 3 -NO 2 16 Cs-A ppd 497 O1-N4 3.11, O3-N4 3.11, O3-O6 3.14 a. See figures for numbering of atoms. The largest dissociation energy of 917 cm -1 was obtained by the O 3 -NH 3 complex due to hydrogen bonding, with two short O-H distances of 2.71 Å. O 3 -H 2 O, also hydrogen bonded, has the next highest D e of 787 cm -1 , with 2.46 Å for the shortest O-H distance. As expected, O 3 -H 2 S has a structure close to O 3 -H 2 O. Its O-H distances are 0.3 to 0.4 Å larger, leading to a correspondingly smaller D e of 629 cm -1 . It is interesting that the most stable isomer of the O 3 -HCN complex is not hydrogen bonded, but instead has N closest to O 3 , with O-N distances of 3.1 to 3.2 Å. This complex has a relatively high D e of 659 cm -1 . The hydrogen bonded C 1 and C 2v complexes, with H closest to O 3 , have slightly lower dissociation energies. The O-H bond distance of 2.57 Å for the C 2v structure of the O 3 -HCN complex (not in Table 6) is close to that of O 3 -H 2 O (2.46 Å). The lowest D e of 353 cm -1 was found for the O 3 -CH 4 complex, much lower than other values in Table 7, despite O-H distances not much larger than for O-NH 3 (2.84 Å vs. 2.71 Å for O 3 -NH 3 ). The largest dissociation energies for complexes of ozone with oxides were found for O 3 -SO 2 with 717 cm -1 , for O 3 -N 2 O with 688 cm -1 and for O 3 -CO 2 with 652 cm -1 . For complexes with oxides bond distances can in most cases not be related to the stability of the complex. Several cases of hydrogen bonding with ozone are represented in these studies. With O 3 -HF added from reference [1], dissociation energies for X-H···O 3 hydrogen bonding with the first-row atoms F, O, N, C are shown in Table 7. Due to decreasing electronegativity of the X atom one expects the strength of H-bonding to decrease in going from X=F to X=C. Such is the case except for O 3 -NH 3 , which has a D e value larger than for O 3 -H 2 O. D e values for hydrogen bonding with O 2 (X-H···O 2 ), in addition to values for bonding with O 3 , have also been included in Table 7 [31]. In hydrogen bonding with O 2 dissociation energies are much smaller (by a factor of about four for F-H to N-H), and they decrease continuously with decreasing electronegativity of X, as one would expect, with D e of O­ 3 -NH 3 below that of O 2 -H 2 O. In the last two rows of Table 7 D e values for complexes of ozone with HCl and H 2 S have been added. As expected, they are well below the values for corresponding first row atoms, especially for O 3 -HCl (close to one half compared to O 3 -HF). The X-H···O angles for complexes with ozone change from near-linear 171 o for F-H···O, to 112 o for O-H···O, to 87 o for N-H···O, and to 104 o for C-H···O. Table 7 Categories of hydrogen bonding with O 3 and O 2 . Dissociation energies D e in cm − 1 for most stable isomers. Type With O 3 D e With O 2 D e F-H···O O 3 -HF 1137 O 2 -HF 301 O-H···O O 3 -H 2 O 787 O 2 -H 2 O 222 N-H···O O 3 -NH 3 917 O 2 -NH 3 196 C-H···O O 3 -CH 4 353 O 2 -CH 4 168 Cl-H···O O 3 -HCl 647 --- --- S-H···O O 3 -H 2 S 629 --- --- Large frequency shifts were obtained for the vibrational frequencies of several complexes. The largest changes occur for the O 3 dimer, with red shifts up to 51 cm − 1 and blue shifts up to 25 cm − 1 (for the antisymmetric stretching band). Larger frequency shifts are also seen for the O 3 -NH 3 (+ 12 cm − 1 ), O 3 -HCN (+ 10 cm − 1 ), O 3 -H 2 O (-9 cm − 1 ) and O 3 -N 2 O (+ 8 cm − 1 ) complexes. At lower levels of basis set the C 1 structure of the O 3 -O 3 complex is calculated to be more stable than the C i structure. However, at the highest level (AVQZ) the dissociation energies of the C 1 and C i isomers are very close (559 cm − 1 for C 1 , 556 cm − 1 for C i ), despite significant differences in structure, such as shorter O-O distances in the C 1 isomer. Based on these results, it cannot be decided which structure is more stable. Extrapolation of dissociation energies to the complete basis set favor C i . Summary High-level theoretical methods were applied to obtain stable structures and properties for complexes of ozone with selected triatomic molecules, as well as with ammonia and methane. The largest dissociation energy was obtained for the hydrogen bonded O 3 -NH 3 complex, larger than for O 3 -H 2 O. Large dissociation energies were obtained also for complexes of ozone with SO 2 , N 2 O, HCN and CO 2 . Hydrogen bonding with O 3 is compared to hydrogen bonding with O 2 . Dissociation energies for complexes with O 3 are two to four times larger than for complexes with O 2 . C 1 and C i structures of the ozone dimer have nearly the same dissociation energies. Calculated shifts in vibrational frequencies are large for the ozone dimer, especially for the antisymmetric stretching band of ozone. Declarations Acknowledgements Provision of adequate computing facilities by the Digital Research Alliance of Canada is much appreciated. Thanks to Prof. S. D. Peyerimhoff for reading the manuscript and commenting on it. Author contribution All work was done by the author. Funding No funding was received for this work. Availability of data and material All data are available upon request. Code availability No new code was used in this work. Conflict of interest The author declares no competing interests. References Grein F (2022) Ab initio studies on complexes of ozone with diatomic molecules, Structural Chemistry. Published Online. https://doi.org/10.1007/s11224-022-02007-w Cížek J (1969) Advances in Chemical Physics, Ed. P. C. 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structure\u003c/p\u003e","description":"","filename":"floatimage14.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-2202310/v1/72ac9bb6516ca654f3b83728.jpeg"},{"id":28579538,"identity":"3e4ae97b-df31-4975-a313-f95da27aa325","added_by":"auto","created_at":"2022-11-02 19:36:09","extension":"jpeg","order_by":15,"title":"Figure 15","display":"","copyAsset":false,"role":"figure","size":14338,"visible":true,"origin":"","legend":"\u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO complex in Cs-B inpl-O structure\u0026nbsp;\u003c/p\u003e","description":"","filename":"floatimage15.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-2202310/v1/60c8b686c77804cf0c4f90b9.jpeg"},{"id":28578384,"identity":"45cdc124-ed86-43bf-a2f5-e72f3e3b28ff","added_by":"auto","created_at":"2022-11-02 19:28:09","extension":"jpeg","order_by":16,"title":"Figure 16","display":"","copyAsset":false,"role":"figure","size":10018,"visible":true,"origin":"","legend":"\u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-NO\u003csub\u003e2\u003c/sub\u003e complex in Cs-A ppd structure\u003c/p\u003e","description":"","filename":"floatimage16.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-2202310/v1/8f08839b47ab3be190ac3b57.jpeg"},{"id":29321589,"identity":"d4fb4bb8-9d87-440c-89b5-798e8a97ae4a","added_by":"auto","created_at":"2022-11-21 09:29:49","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":542603,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-2202310/v1/3b5bab3d-8db6-48db-83bf-8a976c102703.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Ab initio studies on complexes of ozone with triatomic and larger molecules. ","fulltext":[{"header":"Introduction","content":"\u003cp\u003eFollowing a recent study on complexes of ozone with diatomic molecules [1], in the present paper complexes of ozone with the triatomic molecules H\u003csub\u003e2\u003c/sub\u003eO, H\u003csub\u003e2\u003c/sub\u003eS, HCN, CO\u003csub\u003e2\u003c/sub\u003e, O\u003csub\u003e3\u003c/sub\u003e, SO\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003eO, NO\u003csub\u003e2\u003c/sub\u003e, as well as with NH\u003csub\u003e3\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e, are to be investigated. All these molecules are present in the atmosphere. Most of them, in particular O\u003csub\u003e3\u003c/sub\u003e, CO\u003csub\u003e2\u003c/sub\u003e, SO\u003csub\u003e2\u003c/sub\u003e, NO\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003eO, NH\u003csub\u003e3\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e, are considered to be air pollutants, causing problems to human health and plant life. They are also related to climate change. Ozone it is a powerful oxidizer in reacting with other surrounding molecules. Complexes with ozone are often the first step in forthcoming chemical reactions.\u003c/p\u003e \u003cp\u003eSeveral of the systems covered here have received prior attention in the literature. In particular, the O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO complex was studied early on due to its significance in atmospheric reactions, with experimental and theoretical studies being available.\u003c/p\u003e \u003cp\u003eThe aim of this work is the search for the most stable isomers of each system. While in principle large multidimensional potential surfaces would be required for each complex, such is not practical when properties of many systems \u0026ndash; in the present case many complexes with ozone - are to be compared and to be contrasted.\u003c/p\u003e \u003cp\u003eHydrogen bonding (or potentially hydrogen bonding) is involved in complexes of ozone with H\u003csub\u003e2\u003c/sub\u003eO, H\u003csub\u003e2\u003c/sub\u003eS, HCN, NH\u003csub\u003e3\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e, and \u0026ldquo;oxygen bonding\u0026rdquo; is seen in complexes with O\u003csub\u003e3\u003c/sub\u003e, CO\u003csub\u003e2\u003c/sub\u003e, SO\u003csub\u003e2\u003c/sub\u003e, NO\u003csub\u003e2\u003c/sub\u003e and N\u003csub\u003e2\u003c/sub\u003eO.\u003c/p\u003e \u003cp\u003eThe study of a large number of ozone complexes at a high level of theory will allow for interesting and important comparisons to be made.\u003c/p\u003e"},{"header":"Computational Methods And Symmetry Considerations","content":"\u003cp\u003eCoupled cluster singles, doubles and perturbative triples CCSD(T) methods [2, 3] were used, with augmented correlation consistent aug-cc-pVXZ (AVXZ) basis sets [4, 5]. All geometry optimizations were performed with the AVQZ basis set, keeping in most cases the geometry of the monomers held fixed at their respective optimized monomer values. Dissociation energies were corrected for the basis set superposition error (BSSE), as calculated by the method of Boys and Bernardi [6]. In several cases extrapolations to the complete basis set (CBS) limit were performed. They are based on the exponential method proposed by Halkier et al. [7], using CCSD(T)/AVXZ energies with X\u0026thinsp;=\u0026thinsp;D, T, Q. Harmonic vibrational frequencies were obtained by the CCSD(T)/AVDZ method, having all geometry parameters optimized. Calculations are performed using the Gaussian 16 [8] computer programs.\u003c/p\u003e\n\u003cp\u003eMany of the complexes have C\u003csub\u003es\u003c/sub\u003e symmetry. There are two planes of symmetry to be considered. One, named Cs-A, is the plane of the ozone molecule, whereas the other, named Cs-B, is the plane perpendicular to the plane of ozone. In the Cs-A case, the other monomer can be in cis (Cs-A-cis) or trans (Cs-A-trans) orientation relative to O\u003csub\u003e3\u003c/sub\u003e. Another possibility is atom A of an AB\u003csub\u003e2\u003c/sub\u003e molecule to be located in the plane of ozone whereas the two B atoms are positioned above and below this plane, such as to retain C\u003csub\u003es\u003c/sub\u003e symmetry (Cs-A ppd). For complexes with Cs-B symmetry, the other monomer may lie in the Cs-B plane (Cs-B inpl), or for AB\u003csub\u003e2\u003c/sub\u003e molecules be oriented perpendicular to this plane (Cs-B ppd).\u003c/p\u003e\n\u003ch3\u003eStructures And Dissociation Energies For Complexes Of Ozone With Ho, Hs, Hcn, Nh And Ch\u003c/h3\u003e\n\u003cp\u003eIn Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e CCSD(T)/AVQZ calculated dissociation energies are given for complexes of ozone with the hydrides H\u003csub\u003e2\u003c/sub\u003eO, H\u003csub\u003e2\u003c/sub\u003eS, HCN, NH\u003csub\u003e3\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e.\u0026nbsp;\u003c/p\u003e\n\u003ctable border=\"1\" id=\"Tab1\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eDissociation energies D\u003csub\u003ee\u003c/sub\u003e (cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for complexes of ozone with H\u003csub\u003e2\u003c/sub\u003eO, H\u003csub\u003e2\u003c/sub\u003eS, HCN, NH\u003csub\u003e3\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e. BSSE corrected CCSD(T)/AVQZ results.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSystem\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSymmetry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eH\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e787.2\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B ppd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e765.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e736.6\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A trans\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e681.4\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A cis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e680.3\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eH\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e629.0\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B ppd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e609.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A cis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e440.0\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e390.7\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A trans\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e350.8\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eHCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eNCH-Cs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e659.0\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-HCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e632.8\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-HCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e2v\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e625.4\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eNH\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B O\u003csub\u003e3\u003c/sub\u003e:HNH\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e917.5\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B O\u003csub\u003e3\u003c/sub\u003e:H3N\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e209.3\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eCH\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B HCH\u003csub\u003e3\u003c/sub\u003e:O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e352.6\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B H\u003csub\u003e3\u003c/sub\u003eCH:O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e320.3\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cdiv class=\"Section2\" id=\"Sec4\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO complex\u003c/h2\u003e\n \u003cp\u003eComplexes of ozone with water received much attention in the literature. Microwave [9] and infrared spectroscopy [10] studies were performed early on. For a review up to 2005 see Sennikov et al. [11]. There are also several theoretical treatments. The most recent ones are by Anglada et al. [12], Kumar and Sathyamurthy [13], Wang et al. [14] and Hui and Lemke [15].\u003c/p\u003e\n \u003cp\u003eIn the present work, in agreement with literature results, a C\u003csub\u003e1\u003c/sub\u003e conformer (Fig. \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e) is found to be most stable, having D\u003csub\u003ee\u003c/sub\u003e=787 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. The Cs-B ppd structure (Fig. \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e) with a D\u003csub\u003ee\u003c/sub\u003e of 765 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and the Cs-B inplane structure (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e) with D\u003csub\u003ee\u003c/sub\u003e=737 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e have dissociation energies close to the value for C\u003csub\u003e1\u003c/sub\u003e. Cs-B inplane represents a transition state for H\u003csub\u003e2\u003c/sub\u003eO in C\u003csub\u003e1\u003c/sub\u003e symmetry to move through the Cs-B plane from one side to the other. This is likely the C\u003csub\u003es\u003c/sub\u003e structure proposed by microwave studies [9]. For the fully planar Cs-A cis and the Cs-A trans structures D\u003csub\u003ee\u003c/sub\u003e values of 680 and 681 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively, were obtained. The Cs-A cis structure corresponds to a transition state for the C\u003csub\u003e1\u003c/sub\u003e conformer to move from above to below the O\u003csub\u003e3\u003c/sub\u003e plane.\u003c/p\u003e\n \u003cp\u003eComparisons of calculated dissociation energies with values obtained by Anglada et al. [12], using the CCSD(T)/CBS//QCISD/AVTZ method, by Kumar and Sathyamurthy [13], using the CCSD(T)/AVQZ //CCSD(T)/AVTZ method, and by Hui and Lemke [15], using the CCSD(T)/AVQZ method with CBS (DTQ), are shown in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. Most results are within 50 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eof the present ones.\u0026nbsp;\u003c/p\u003e\n \u003ctable border=\"1\" id=\"Tab2\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eComparison of calculated dissociation energies D\u003csub\u003ee\u003c/sub\u003e (in cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO complexes with literature values.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eStructure\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003ePresent\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eAnglada et al. [12]\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eKumar et al. [13]\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eHui et al. [15]\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e787\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e836 (A4)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e762 (leg)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e804\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B ppd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e765\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e794 (A5)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e766 (eclips)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e---\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e737\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e---\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e734 (dipole)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e---\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A trans\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e681\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e717 (A3)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e637 (trans)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e616\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A cis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e680\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e703 (A1)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e682 (cis)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e612\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003c/p\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec5\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS complex\u003c/h2\u003e\n \u003cp\u003eComplexes of ozone with hydrogen sulfide H\u003csub\u003e2\u003c/sub\u003eS have structures and energetic relationships very similar to O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO complexes. Dissociation energies for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS complexes are about 150 to 300 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e lower than for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO. Most stable is a C\u003csub\u003e1\u003c/sub\u003e structure (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e), close in geometry to C\u003csub\u003e1\u003c/sub\u003e of O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO (with D\u003csub\u003ee\u003c/sub\u003e of 629 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e vs. 787 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO), followed by the Cs-B ppd structure (609 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e vs 711 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO). Dissociation energies for the cis and trans structures are 440 and 351 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively, again 200 to 300 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e lower than for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO.\u003c/p\u003e\n \u003cp\u003eVahedpour et al. [16] studied the atmospheric reaction of O\u003csub\u003e3\u003c/sub\u003e with H\u003csub\u003e2\u003c/sub\u003eS, showing by B3LYP/6-311\u0026thinsp;+\u0026thinsp;+\u0026thinsp;G(3df,3pd) calculations that O\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003eS forms a stable complex. Starting from this complex, over a series of intermediate products, H\u003csub\u003e2\u003c/sub\u003eO\u0026thinsp;+\u0026thinsp;SO\u003csub\u003e2\u003c/sub\u003e is obtained. The BSSE corrected dissociation energy for the O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS complex is given as 482 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, having a geometry close to the C\u003csub\u003e1\u003c/sub\u003e geometry obtained here.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec6\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-HCN complex\u003c/h2\u003e\n \u003cp\u003eMielke and Andrews [17] performed infrared studies on the O\u003csub\u003e3\u003c/sub\u003e-HCN complex observing a number of new bands. The complex was assumed to have C\u003csub\u003e2v\u003c/sub\u003e symmetry.\u003c/p\u003e\n \u003cp\u003eUsing the CCSD(T) method the Cs-B inplane structure with N closest to O\u003csub\u003e3\u003c/sub\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e) is most stable (659 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). This is followed by the C\u003csub\u003e1\u003c/sub\u003e (633 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and C\u003csub\u003e2v\u003c/sub\u003e (625 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e) conformers having hydrogen closest to O\u003csub\u003e3\u003c/sub\u003e. Despite large differences in geometry, all three structures are calculated to have similar dissociation energies.\u003c/p\u003e\n \u003cp\u003eIn a theoretical study on C-H\u0026middot;\u0026middot;\u0026middot;O hydrogen bonded complexes, Turi and Dannenberg [18] performed calculations on the O\u003csub\u003e3\u003c/sub\u003e-HCN complex. Using the MP2/D95++(d,p) method they obtained a counterpoise corrected dissociation energy of 1.76 kcal/mol (616 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for the C\u003csub\u003e2v\u003c/sub\u003e structure.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec7\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e complex\u003c/h2\u003e\n \u003cp\u003eMany different structure\u003cstrong\u003es\u003c/strong\u003e of the O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e complex were investigated. The by far most stable structure has O\u003csub\u003e3\u003c/sub\u003e facing NH\u003csub\u003e3\u003c/sub\u003e in Cs-B symmetry, with NH\u003csub\u003e3\u003c/sub\u003e tilted such that one hydrogen points towards O\u003csub\u003e3\u003c/sub\u003e (Cs-B O\u003csub\u003e3\u003c/sub\u003e:HNH\u003csub\u003e2\u003c/sub\u003e, Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e). It has a large dissociation energy of 917 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and no imaginary frequencies. All other structurers considered are much less stable. For example, the one with O\u003csub\u003e3\u003c/sub\u003e facing the three hydrogens of NH\u003csub\u003e3\u003c/sub\u003e, also having C\u003csub\u003es\u003c/sub\u003e symmetry (Cs-B O\u003csub\u003e3\u003c/sub\u003e:H\u003csub\u003e3\u003c/sub\u003eN), has D\u003csub\u003ee\u003c/sub\u003e=209 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. According to calculated vibrational frequencies, it is not stable. Structures with N of NH\u003csub\u003e3\u003c/sub\u003e facing the central oxygen of ozone (O\u003csub\u003e3\u003c/sub\u003e turned away), as well as a \u0026ldquo;hydrogen bonded\u0026rdquo; structure with N-H-O-O-O in the same plane, have very low dissociation energies.\u003c/p\u003e\n \u003cp\u003eLucchese et al. [19] performed SCF calculations with a minimal basis set on the NH\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e and NH\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e complexes. For the NH\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e complex with a simplified geometry (O\u003csub\u003e3\u003c/sub\u003e facing N of NH\u003csub\u003e3\u003c/sub\u003e but not tilted, O3:NH3) they obtained a dissociation energy of 2.24 kcal/mol, or 783 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e\n \u003cp\u003eAsgharzade and Vahedpour [20] reported B3LYP results for tropospheric oxidation reactions, including the NH\u003csub\u003e3\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;O\u003csub\u003e3\u003c/sub\u003e reaction. Starting from the most stable O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e complex leads in a series of steps to HO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003eNO, but starting from the O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e3\u003c/sub\u003eN complex leads to HO\u003csub\u003e2\u003c/sub\u003e\u0026thinsp;+\u0026thinsp;NO\u0026thinsp;+\u0026thinsp;H\u003csub\u003e2\u003c/sub\u003e. Their CCSD(T)//B3LYP/6-311\u0026thinsp;+\u0026thinsp;+\u0026thinsp;G (3df, 3pd) results are 1.41 kcal/mol (493 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for the O3:NH3 complex (again not tilted), and 0.57 kcal/mol (199 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for the O\u003csub\u003e3\u003c/sub\u003e:H\u003csub\u003e3\u003c/sub\u003eN complex.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec8\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e complex\u003c/h2\u003e\n \u003cp\u003eThe most stable structure of the O\u003csub\u003e3\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e complex has Cs-B symmetry, with O\u003csub\u003e3\u003c/sub\u003e facing three hydrogens of CH\u003csub\u003e4\u003c/sub\u003e (Cs-B CH3-O3, D\u003csub\u003ee\u003c/sub\u003e=353 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003e). O-CH2 is located in the Cs-B plane, with the other oxygens and hydrogens lying above and below this plane. Another structure, with O\u003csub\u003e3\u003c/sub\u003e facing two hydrogens of CH\u003csub\u003e4\u003c/sub\u003e, also in Cs-B symmetry, has D\u003csub\u003ee\u003c/sub\u003e=320 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e\n \u003cp\u003eWalker et al [21] performed Fourier-transform microwave studies on the O\u003csub\u003e3\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e complex. They found the complex to have a plane of symmetry, corresponding to the C\u003csub\u003es\u003c/sub\u003e plane found here. They reported the shortest C-O distance to be 3.57 \u0026Aring;, compared to 3.24 \u0026Aring; calculated here for the most stable structure.\u003c/p\u003e\n\u003c/div\u003e\n\u003ch3\u003e\u003cstrong\u003eStructures and dissociation energies for complexes of ozone with CO\u003csub\u003e2\u003c/sub\u003e, O\u003csub\u003e3\u003c/sub\u003e, SO\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003eO, NO\u003csub\u003e2\u003c/sub\u003e\u003c/strong\u003e\u003c/h3\u003e\n\u003cp\u003eIn Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e CCSD(T)/AVQZ calculated dissociation energies are given for complexes of ozone with CO\u003csub\u003e2\u003c/sub\u003e, O\u003csub\u003e3\u003c/sub\u003e, SO\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003eO and NO\u003csub\u003e2\u003c/sub\u003e.\u0026nbsp;\u003c/p\u003e\n\u003ctable border=\"1\" id=\"Tab3\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eDissociation energies D\u003csub\u003ee\u003c/sub\u003e (cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for complexes of ozone with CO\u003csub\u003e2\u003c/sub\u003e, O\u003csub\u003e3\u003c/sub\u003e, SO\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003eO and NO\u003csub\u003e2\u003c/sub\u003e. BSSE corrected CCSD(T)/AVQZ results.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSystem\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSymm/Struct.\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e-CCSD(T)\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e2v\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e651.7\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A trans\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e467.6\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A cis\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e394.7\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e559.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003ei\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e556.2\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e500.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A ppd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e462.2\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eSO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e716.9\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A ppd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e636.6\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e513.6\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B ppd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e510.0\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl-O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e688.0\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl-N1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e560.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl-N2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e242.5\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e\u003cstrong\u003e-\u003c/strong\u003eNO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A ppd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e496.9\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"3\"\u003ea. CBS value is 676.9 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003c/p\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cdiv class=\"Section2\" id=\"Sec10\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e complex\u003c/h2\u003e\n \u003cp\u003eThe most stable O\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e complex has a C\u003csub\u003e2v\u003c/sub\u003e structure (Fig. \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003e) with a dissociation energy of 652 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. At all levels of basis set but before BSSE corrections, a Cs-B inpl structure has a slightly lower energy (only 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) than the C\u003csub\u003e2v\u003c/sub\u003e structure. However, due to its lower BSSE value, the C\u003csub\u003e2v\u003c/sub\u003e isomer becomes more stable after BSSE correction. Fully planar structures are Cs-A cis with D\u003csub\u003ee\u003c/sub\u003e=395 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and Cs-A trans with D\u003csub\u003ee\u003c/sub\u003e=468 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Cs-A cis has a quadrupolar alignment, with CO\u003csub\u003e2\u003c/sub\u003e shifted nearly parallel relative to O\u003csub\u003e3\u003c/sub\u003e.\u003c/p\u003e\n \u003cp\u003eThe dissociation energy for the C\u003csub\u003e2v\u003c/sub\u003e conformer extrapolated to the complete basis set is 677 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, compared to the BSSE adjusted CCSD(T) value of 652 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e\n \u003cp\u003eSeif et al. [22] obtained BSSE corrected dissociation energies of 6.87 kJ/mol or 574 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the C\u003csub\u003e2v\u003c/sub\u003e (or Cs-B inplane, not clear) structure and 4.40 kJ/mol or 368 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the Cs-A trans structure, using the MP2/AVDZ method.\u003c/p\u003e\n \u003cp\u003eFor the most stable (planar) structure of the CO\u003csub\u003e2\u003c/sub\u003e complex with the oxygen molecule a dissociation energy of 230 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was found [23].\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec11\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e complex\u003c/h2\u003e\n \u003cp\u003eFrom CCSD(T)/AVDZ potential energy surfaces, Azofra et al. [24] found five stable minima for the ozone dimer, having CCSD(T)/AVTZ dissociation energies of 2.24 kcal/mol (783 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for the C\u003csub\u003ei\u003c/sub\u003e structure, 1.89 kcal/mol (661 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for the Cs-B inplane structure, and much lower dissociation energies for the remaining structures.\u003c/p\u003e\n \u003cp\u003eGadzhiev et al. [25] studied the oxygen allotropes O\u003csub\u003en\u003c/sub\u003e (n\u0026thinsp;\u0026le;\u0026thinsp;6), including the O\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e complex. Calculated CCSD(T)/cc-pCVTZ (C for additional core orbitals) dissociation energies are 8.3 kJ/mol or 694 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the C\u003csub\u003ei\u003c/sub\u003e structure, and 7.3 kJ/mol or 610 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the Cs-B inplane structure.\u003c/p\u003e\n \u003cp\u003eStudying homo- and heterodimers of sulphur dioxide and ozone Ford [26] obtained a BSSE corrected dissociation energy of 11.21 kJ/mol or 937 cm-1 for the C\u003csub\u003ei\u003c/sub\u003e structure of the ozone dimer, using the MP2/AVTZ method.\u003c/p\u003e\n \u003cp\u003eIn the present investigation, the C\u003csub\u003ei\u003c/sub\u003e structure and other structures were investigated for singlet O\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e. By the CCSD(T)/AVQZ method a BSSE corrected dissociation energy of 556 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was obtained for the C\u003csub\u003ei\u003c/sub\u003e isomer (Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e). However, due to one imaginary frequency found for this structure (by both MP2 and CCSD(T) methods, using various basis sets) a C\u003csub\u003e1\u003c/sub\u003e structure (Fig. \u003cspan class=\"InternalRef\"\u003e11\u003c/span\u003e) was also investigated, having relaxed symmetry constraints. Its CCSD(T)/AVQZ BSSE corrected dissociation energy is almost the same, 559 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e\n \u003cp\u003eCCSD(T) results for C\u003csub\u003ei\u003c/sub\u003e and C\u003csub\u003e1\u003c/sub\u003e structures using AVDZ to AVQZ basis sets are shown in Table \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e. Before BSSE corrections, the C\u003csub\u003e1\u003c/sub\u003e structures are much more stable than their C\u003csub\u003ei\u003c/sub\u003e counterparts. For both structures D\u003csub\u003ee\u003c/sub\u003e and BSSE values decrease as the basis set is increased. For each basis set, D\u003csub\u003ee\u003c/sub\u003e and BSSE values are higher for C\u003csub\u003e1\u003c/sub\u003e than for C\u003csub\u003ei\u003c/sub\u003e, due to shorter interatomic distances in C\u003csub\u003e1\u003c/sub\u003e. However, with BSSE values decreasing faster than D\u003csub\u003ee\u003c/sub\u003e values, the BSSE corrected dissociation energies increase rather than decrease. For AVDZ and AVTZ the C\u003csub\u003e1\u003c/sub\u003e values are markedly higher than the C\u003csub\u003ei\u003c/sub\u003e values. At the highest level of basis set, however, the BSSE corrected D\u003csub\u003ee\u003c/sub\u003e values for C\u003csub\u003ei\u003c/sub\u003e and C\u003csub\u003e1\u003c/sub\u003e are about the same, 556 and 559 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively.\u0026nbsp;\u003c/p\u003e\n \u003ctable border=\"1\" id=\"Tab4\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eCalculated dissociation energies D\u003csub\u003ee\u003c/sub\u003e (cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for the C\u003csub\u003ei\u003c/sub\u003e and C\u003csub\u003e1\u003c/sub\u003e structures of O\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e before and after BSSE correction.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eMethod\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colspan=\"3\"\u003e\n \u003cp\u003eC\u003csub\u003ei\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colspan=\"3\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\u0026nbsp;\u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eBSSE\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e -BSSE\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eBSSE\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e -BSSE\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCCSD(T)/AVDZ\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e733.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e324.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e409.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e819.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e373.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e445.8\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCCSD(T)/AVTZ\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e661.9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e167.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e494.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e782.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e216.6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e555.7\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCCSD(T)/AVQZ\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e593.3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e37.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e556.2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e651.8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e92.7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e559.1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003c/p\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n \u003cp\u003eOn account of the nearly equal dissociation energies of the C\u003csub\u003ei\u003c/sub\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e10\u003c/span\u003e) and C\u003csub\u003e1\u003c/sub\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e11\u003c/span\u003e) conformers as obtained by the CCSD(T) method, a decision on which is the leading structure cannot be made. CBS values calculated by the exponential method are 533 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for C\u003csub\u003ei\u003c/sub\u003e and 516 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for C\u003csub\u003e1\u003c/sub\u003e, favoring the C\u003csub\u003ei\u003c/sub\u003e structure as being more stable. The C\u003csub\u003e1\u003c/sub\u003e structure has a quadrupolar arrangement, with the two ozone molecules shifted parallel relative to each other, allowing for shorter O-O distances (see later).\u003c/p\u003e\n \u003cp\u003eIn addition to the C\u003csub\u003e1\u003c/sub\u003e and C\u003csub\u003ei\u003c/sub\u003e structures, results were obtained for the Cs-B inplane (500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and Cs-A ppd (462 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, Fig. \u003cspan class=\"InternalRef\"\u003e12\u003c/span\u003e) structures.\u003c/p\u003e\n \u003cp\u003eDissociation energies for the C\u003csub\u003ei\u003c/sub\u003e and Cs-B inplane structures obtained by Azofra et al. [24] and Gadziev et al. [25] are much larger than found here. It appears that in both cases BSSE corrections were not applied.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec12\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e complex\u003c/h2\u003e\n \u003cp\u003eSulfur dioxide, SO\u003csub\u003e2\u003c/sub\u003e, is released into the atmosphere when sulfur containing fuels are burned. The structures of the O\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e complex are quite similar to those of the ozone dimer. Most stable is a C\u003csub\u003e1\u003c/sub\u003e structure (Fig. \u003cspan class=\"InternalRef\"\u003e13\u003c/span\u003e) with a dissociation energy of 717 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. This is followed by the Cs-A ppd conformer with 637 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e14\u003c/span\u003e) and by Cs-B inpl (514 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). The Cs-B ppd structure corresponds to the C\u003csub\u003ei\u003c/sub\u003e structure of the ozone dimer. It has a D\u003csub\u003ee\u003c/sub\u003e of 510 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Cs-A cis and trans structures are much less stable.\u003c/p\u003e\n \u003cp\u003eUsing the MP2/AVTZ method Ford [27] obtained a BSSE corrected value of 12.18 kJ/mol or 1018 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the C\u003csub\u003e1\u003c/sub\u003e structure. Azofra and Scheiner [27] performed CCSD(T)/AVTZ calculations on dimers, trimers and tetramers of SO\u003csub\u003e2\u003c/sub\u003e with CO\u003csub\u003e2\u003c/sub\u003e. The SO\u003csub\u003e2\u003c/sub\u003e dimer (corresponding to the O\u003csub\u003e3\u003c/sub\u003e dimer) was found to have a large dissociation energy of 1056 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec13\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO complex\u003c/h2\u003e\n \u003cp\u003eThe O\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO complex is of interest, as nitrous oxide may be one of the most ozone depleting substances in the atmosphere [28].\u003c/p\u003e\n \u003cp\u003eThree structures of the O\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO complex were found to be stable. All have C\u003csub\u003es\u003c/sub\u003e symmetry. They belong to the Cs-B inplane category, with N\u003csub\u003e2\u003c/sub\u003eO lying in the plane perpendicular to the plane of ozone. The differences consist in either the oxygen (Cs-B inpl-O, D\u003csub\u003ee\u003c/sub\u003e=688 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), the terminal nitrogen (Cs-B inpl-N1, D\u003csub\u003ee\u003c/sub\u003e=560 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) or the central nitrogen (Cs-B inpl-N2, D\u003csub\u003ee\u003c/sub\u003e=243 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) of N\u003csub\u003e2\u003c/sub\u003eO being closest to the central oxygen of ozone. The structure with the oxygen of N\u003csub\u003e2\u003c/sub\u003eO closest to ozone (Fig. \u003cspan class=\"InternalRef\"\u003e15\u003c/span\u003e) has the highest dissociation energy. Cis and trans structures with N\u003csub\u003e2\u003c/sub\u003eO lying in the plane of ozone have dissociation energies in the range of 200 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Several structures in C\u003csub\u003e1\u003c/sub\u003e symmetry were also considered. They optimized to close lying C\u003csub\u003es\u003c/sub\u003e structures.\u003c/p\u003e\n \u003cp\u003eNo literature could be found on the O\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO complex. The N\u003csub\u003e2\u003c/sub\u003eO complex with O\u003csub\u003e2\u003c/sub\u003e was discussed by Salmon and Lane [29]. Its structure was found to be planar slipped parallel, having a CCSD(T)-F12b/AVQZ dissociation energy of 280 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv class=\"Section2\" id=\"Sec14\"\u003e\n \u003ch2\u003eO\u003csub\u003e3\u003c/sub\u003e-NO\u003csub\u003e2\u003c/sub\u003e complex\u003c/h2\u003e\n \u003cp\u003eNO\u003csub\u003e2\u003c/sub\u003e, nitrogen dioxide, is formed when fossil fuels are burned, and is released into the atmosphere, where it constitutes one of the major air pollutants. Calculations on many different structures of the O\u003csub\u003e3\u003c/sub\u003e-NO\u003csub\u003e2\u003c/sub\u003e complex were attempted. However, only in one case could geometry optimizations be completed. This structure, with D\u003csub\u003ee\u003c/sub\u003e=497 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, has Cs-A ppd symmetry, with N lying in the plane of ozone, and the O\u0026rsquo;s of NO\u003csub\u003e2\u003c/sub\u003e lying above and below this plane (Fig. \u003cspan class=\"InternalRef\"\u003e16\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eIt is possible that other structures of the O\u003csub\u003e3\u003c/sub\u003e-NO\u003csub\u003e2\u003c/sub\u003e complex have lower energies. Such is indicated by the structure found having one imaginary frequency.\u003c/p\u003e\n\u003c/div\u003e\n\u003ch3\u003eHarmonic Vibrational Frequencies\u003c/h3\u003e\n\u003cp\u003eIn Table \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003eharmonic vibrational frequencies are given for ozone complexes in their most stable structures.\u0026nbsp;\u003c/p\u003e\n\u003ctable border=\"1\" id=\"Tab5\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 5\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eHarmonic vibrational frequencies (cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and frequency shifts (cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for most stable O\u003csub\u003e3\u003c/sub\u003e-ABC complexes. CCSD(T)/AVDZ results.\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eComplex\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eSymmetry\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colspan=\"3\"\u003e\n \u003cp\u003eOzone frequencies\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colspan=\"2\"\u003e\n \u003cp\u003eABC frequencies\u003csup\u003eb\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\u0026nbsp;\u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e709\u0026thinsp;+\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e973\u0026thinsp;+\u0026thinsp;2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1118\u0026thinsp;+\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1636 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3779 -9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3895 -10\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e706 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e968 -3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1116 -1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1187 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2693\u0026thinsp;+\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2714\u0026thinsp;+\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-HCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e706 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e981\u0026thinsp;+\u0026thinsp;10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1121\u0026thinsp;+\u0026thinsp;4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e698\u0026thinsp;+\u0026thinsp;5\u003csup\u003ec\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2083\u0026thinsp;+\u0026thinsp;6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3417\u0026thinsp;+\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-HCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC2v\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e707 -1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e971 0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1116 -1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e727 +34\u003c/p\u003e\n \u003cp\u003e769\u0026thinsp;+\u0026thinsp;76\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2077 0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3395 -21\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B O3:HNH2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e708 0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e979\u0026thinsp;+\u0026thinsp;8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1121\u0026thinsp;+\u0026thinsp;4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1083\u0026thinsp;+\u0026thinsp;12\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1648 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3432 -3\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B HCH3:O3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e704 -4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e965 -6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1115 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1321\u0026thinsp;+\u0026thinsp;2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1537\u0026thinsp;+\u0026thinsp;3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e3041 -3\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e714 +6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e968 -3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1117 0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e656 -3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1317 +1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2341 +1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e703 -5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e927\u0026thinsp;\u0026minus;\u0026thinsp;44\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1115 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e704 -4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e991\u0026thinsp;+\u0026thinsp;20\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1115 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003ei\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e705 -3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e920\u0026thinsp;\u0026minus;\u0026thinsp;51\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1114 -3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e706 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e996\u0026thinsp;+\u0026thinsp;25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1116 -1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e704 -4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e971 0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1116 -1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e705 -3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e972\u0026thinsp;+\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1117 0\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e708 0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e969 -2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1117 0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e476\u0026thinsp;+\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1051\u0026thinsp;+\u0026thinsp;4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1213\u0026thinsp;+\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl-O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e703 -5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e973\u0026thinsp;+\u0026thinsp;2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1116 -1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e563 -4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e1282\u0026thinsp;+\u0026thinsp;5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e2249\u0026thinsp;+\u0026thinsp;8\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003c/p\u003e\n\u003cp\u003ea. For NH\u003csub\u003e3\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e only frequencies with the largest changes are given.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eb. Shown are frequencies calculated for the complex and their differences from frequencies of the isolated monomers, + for blue shifts, - for red shifts. \u0026nbsp;The ozone frequencies are 708 cm\u003csup\u003e-1\u003c/sup\u003e (A\u003csub\u003e1\u003c/sub\u003e), 971 cm\u003csup\u003e-1\u003c/sup\u003e (B\u003csub\u003e2\u003c/sub\u003e) and 1117 cm\u003csup\u003e-1\u003c/sup\u003e (A\u003csub\u003e1\u003c/sub\u003e).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003ec. Same result for the other component. \u0026nbsp; \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFairly large frequency shifts were found for the ozone dimer. In the C\u003csub\u003ei\u003c/sub\u003e complex the ozone B\u003csub\u003e2\u003c/sub\u003e band (971 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e as calculated) is split into frequencies of 920 (-51) and 996 (+\u0026thinsp;25) cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Similar results were obtained for the C\u003csub\u003e1\u003c/sub\u003e isomer of this complex (shifts of -44 and +\u0026thinsp;20 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). Frequency shifts for the C\u003csub\u003ei\u003c/sub\u003e complex calculated by the higher level CCSD(T)/AVTZ method are nearly the same (-47, +\u0026thinsp;21 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the B\u003csub\u003e2\u003c/sub\u003e mode). Infrared studies of the ozone dimer in an argon matrix performed by Bahou et al. [30] found a small blue shift (2 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) as well as a small red shift (3 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for the B\u003csub\u003e2\u003c/sub\u003e band. It is assumed that the conformer observed in the argon matrix was not the C\u003csub\u003ei\u003c/sub\u003e or C\u003csub\u003e1\u003c/sub\u003e conformer but Cs-B inpl instead, for which only small frequency shifts were found (Table \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e).\u003c/p\u003e\n\u003cp\u003eAzofra et al. [24] obtained red shifts only for all five O\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e structures investigated. For the C\u003csub\u003ei\u003c/sub\u003e dimer shifts of -10 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the A\u003csub\u003e1\u003c/sub\u003e, -32 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the A\u003csub\u003e1\u003c/sub\u003e and \u0026minus;\u0026thinsp;111 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the B\u003csub\u003e2\u003c/sub\u003e mode were obtained. Gadzhiev et al. [25] calculated frequency shifts of -34 and +\u0026thinsp;18 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the C\u003csub\u003ei\u003c/sub\u003e dimer, and +\u0026thinsp;2, +4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for Cs-B inpl .\u003c/p\u003e\n\u003cp\u003eFrequency shifts are small for the most stable isomer of O\u003csub\u003e3\u003c/sub\u003e-HCN (Cs-B inpl). However, they are quite large for the C\u003csub\u003e2v\u003c/sub\u003e complex, with shifts of +\u0026thinsp;34 and +\u0026thinsp;76 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the degenerate bending motion at 693 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and \u0026minus;\u0026thinsp;21 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the asymmetric stretch at 3416 cm\u003csup\u003e1\u003c/sup\u003e. Mielke and Andrews [17] observed a shift of -30 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the asymmetric stretch at 3303.8 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, assuming the complex had C\u003csub\u003e2v\u003c/sub\u003e symmetry (compared to -21 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e calculated).\u003c/p\u003e\n\u003cp\u003eOnly small frequency shifts were calculated for the C\u003csub\u003e1\u003c/sub\u003e structure of the O\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e complex, with a blue shift of 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for one of the SO\u003csub\u003e2\u003c/sub\u003e bands.\u003c/p\u003e\n\u003cp\u003eFor the O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e complex blue shifts of 8 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (for the B\u003csub\u003e2\u003c/sub\u003e band of ozone) and 12 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (for the lowest NH\u003csub\u003e3\u003c/sub\u003e bands, N-H wagging) were found. Large blue shifts of 10 and 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the ozone bands, and 5 and 6 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for HCN are seen for the O\u003csub\u003e3\u003c/sub\u003e-HCN complex.\u003c/p\u003e\n\u003cp\u003eLarge red shifts of 9 and 10 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e of the H\u003csub\u003e2\u003c/sub\u003eO bands and small blue shifts (1 and 2 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) of the ozone bands were calculated for the C\u003csub\u003e1\u003c/sub\u003e structure of the O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO complex. By infrared spectroscopy Schriver et al. [10] observed blue shifts of about 5 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the three ozone bands of the O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO complex. For the C\u003csub\u003e1\u003c/sub\u003e structure blue shifts of 3 to 6 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were found for the ozone frequencies, and red shifts of -6 and \u0026minus;\u0026thinsp;7 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the stretching frequencies of H\u003csub\u003e2\u003c/sub\u003eO.\u003c/p\u003e\n\u003cp\u003eKumar and Sathyamurthy [13] gave detailed vibrational frequencies and frequency shifts for the O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO complexes, calculated at the CCSD/AVTZ level of theory.\u003c/p\u003e\n\u003cp\u003eContrary to larger frequency shifts for the O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO complex, only small ones, up to 3 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, were obtained for the O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS complex.\u003c/p\u003e\n\u003cp\u003eFor O\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO the lowest O\u003csub\u003e3\u003c/sub\u003e frequency is red shifted by 5 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, whereas the NO\u003csub\u003e2\u003c/sub\u003e frequencies are red (5 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and blue (5 and 8 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) shifted.\u003c/p\u003e"},{"header":"Discussion","content":"\u003cp\u003eIn Table \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e, dissociation energies and shortest interatomic distances are listed for the most stable isomers of complexes with ozone.\u0026nbsp;\u003c/p\u003e\n\u003ctable border=\"1\" id=\"Tab6\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 6\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eDissociation energies D\u003csub\u003ee\u003c/sub\u003e (cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and shortest interatomic distances (\u0026Aring;) of the most stable isomers of complexes with ozone.\u003csup\u003ea\u003c/sup\u003e\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eComplex\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eFig.\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eStructure\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eShortest distances\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e7\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B O\u003csub\u003e3\u003c/sub\u003e:HNH\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e917\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO6-H2 2.71, O7-H2 2.71, O6-N1 2.91\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e (A4)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e787\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO3-H6 2.46, O2-H6 2.75, O1-H6 2.87\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e13\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e717\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO2-O6 2.99, O2-S4 3.06, O3-O6 3.11\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e15\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B inpl-O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e688\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO2-O6 2.94, O3-O6 2.94, O2-N4 3.04\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-HCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eNCH-Cs-B inpl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e659\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO1-N4 3.09, O2-N4 3.18, O3-N4 3.18\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e9\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e2v\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e652\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO2-C4 3.02, O3-C4 3.02, O2-O5 3.23\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e (A4)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e629\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO3-H5 2.84, O2-H5 2.84, O1-H5 3.12\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-HCN\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e2v\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e625\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO2-H4 2.57, O3-H4 2.57, O1-H4 3.02\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e C\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e11\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e559\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO2-O4 2.75, O3-O6 2.88, O3-O4 3.04\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e C\u003csub\u003ei\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC\u003csub\u003ei\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e556\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO2-O6 2.93, O3-O5 2.93, O1-O6 3.54\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e8\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-B HCH3:O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e353\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO7-H5 2.84 O8-H5 2.84, O6-H5 2.94\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-NO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCs-A ppd\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e497\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO1-N4 3.11, O3-N4 3.11, O3-O6 3.14\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctfoot\u003e\n \u003ctr\u003e\n \u003ctd colspan=\"5\"\u003ea. See figures for numbering of atoms.\u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tfoot\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eThe largest dissociation energy of 917 cm\u003csup\u003e-1\u003c/sup\u003e was obtained by the O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e complex due to hydrogen bonding, with two short O-H distances of 2.71 \u0026Aring;. O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO, also hydrogen bonded, \u0026nbsp;has the next highest D\u003csub\u003ee\u003c/sub\u003e of 787 cm\u003csup\u003e-1\u003c/sup\u003e, with 2.46 \u0026Aring; for the shortest O-H distance. As expected, O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS has a structure close to O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO. Its O-H distances are 0.3 to 0.4 \u0026Aring; larger, leading to a correspondingly smaller D\u003csub\u003ee\u003c/sub\u003e of 629 cm\u003csup\u003e-1\u003c/sup\u003e. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIt is interesting that the most stable isomer of the O\u003csub\u003e3\u003c/sub\u003e-HCN complex is not hydrogen bonded, but instead has N closest to O\u003csub\u003e3\u003c/sub\u003e, with O-N distances of 3.1 to 3.2 \u0026Aring;. This complex has a relatively high D\u003csub\u003ee\u003c/sub\u003e of 659 cm\u003csup\u003e-1\u003c/sup\u003e. The hydrogen bonded C\u003csub\u003e1\u003c/sub\u003e and C\u003csub\u003e2v\u003c/sub\u003e complexes, with H closest to O\u003csub\u003e3\u003c/sub\u003e, have slightly lower dissociation energies.\u0026nbsp;The\u0026nbsp;O-H bond distance of 2.57 \u0026Aring; for the C\u003csub\u003e2v\u003c/sub\u003e structure of the O\u003csub\u003e3\u003c/sub\u003e-HCN complex (not in Table 6) is close to that of O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO (2.46 \u0026Aring;). \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe lowest D\u003csub\u003ee\u003c/sub\u003e of 353 cm\u003csup\u003e-1\u003c/sup\u003e was found for the O\u003csub\u003e3\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e complex, much lower than other values in Table 7, despite O-H distances not much larger than for O-NH\u003csub\u003e3\u003c/sub\u003e (2.84 \u0026Aring; vs. 2.71 \u0026Aring; for O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe largest dissociation energies for complexes of ozone with oxides were found for O\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e with 717 cm\u003csup\u003e-1\u003c/sup\u003e, for O\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO with 688 cm\u003csup\u003e-1\u003c/sup\u003e and for O\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e with 652 cm\u003csup\u003e-1\u003c/sup\u003e. For complexes with oxides bond distances can in most cases not be related to the stability of the complex.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eSeveral cases of hydrogen bonding with ozone are represented in these studies. With O\u003csub\u003e3\u003c/sub\u003e-HF added from reference [1], dissociation energies for X-H\u0026middot;\u0026middot;\u0026middot;O\u003csub\u003e3\u003c/sub\u003e hydrogen bonding with the first-row atoms F, O, N, C are shown in Table 7. Due to decreasing electronegativity of the X atom one expects the strength of H-bonding to decrease in going from X=F to X=C. Such is the case except for O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e, which has a D\u003csub\u003ee\u003c/sub\u003e value larger than for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO. \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e values for hydrogen bonding with O\u003csub\u003e2\u003c/sub\u003e (X-H\u0026middot;\u0026middot;\u0026middot;O\u003csub\u003e2\u003c/sub\u003e), in addition to values for bonding with O\u003csub\u003e3\u003c/sub\u003e, have also been included in Table 7 [31]. In hydrogen bonding with O\u003csub\u003e2\u003c/sub\u003e dissociation energies are much smaller (by a factor of about four for F-H to N-H), and they decrease continuously with decreasing electronegativity of X, as one would expect, with D\u003csub\u003ee\u003c/sub\u003e of O\u0026shy;\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e below that of O\u003csub\u003e2\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eIn the last two rows of Table 7 D\u003csub\u003ee\u003c/sub\u003e values for complexes of ozone with HCl and H\u003csub\u003e2\u003c/sub\u003eS have been added. As expected, they are well below the values for corresponding first row atoms, especially for O\u003csub\u003e3\u003c/sub\u003e-HCl (close to one half compared to O\u003csub\u003e3\u003c/sub\u003e-HF). \u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe X-H\u0026middot;\u0026middot;\u0026middot;O angles for complexes with ozone change from near-linear 171\u003csup\u003eo\u003c/sup\u003e for F-H\u0026middot;\u0026middot;\u0026middot;O, to 112\u003csup\u003eo\u003c/sup\u003e for O-H\u0026middot;\u0026middot;\u0026middot;O, to 87\u003csup\u003eo\u003c/sup\u003e for N-H\u0026middot;\u0026middot;\u0026middot;O, and to 104\u003csup\u003eo\u003c/sup\u003e for C-H\u0026middot;\u0026middot;\u0026middot;O. \u0026nbsp;\u003c/p\u003e\n\u003ctable border=\"1\" id=\"Tab7\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 7\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eCategories of hydrogen bonding with O\u003csub\u003e3\u003c/sub\u003e and O\u003csub\u003e2\u003c/sub\u003e. Dissociation energies D\u003csub\u003ee\u003c/sub\u003e in cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for most stable isomers.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eType\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eWith O\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eWith O\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eD\u003csub\u003ee\u003c/sub\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eF-H\u0026middot;\u0026middot;\u0026middot;O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-HF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1137\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e2\u003c/sub\u003e-HF\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e301\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO-H\u0026middot;\u0026middot;\u0026middot;O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e787\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e2\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e222\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eN-H\u0026middot;\u0026middot;\u0026middot;O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e917\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e196\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eC-H\u0026middot;\u0026middot;\u0026middot;O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e353\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e2\u003c/sub\u003e-CH\u003csub\u003e4\u003c/sub\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e168\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eCl-H\u0026middot;\u0026middot;\u0026middot;O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-HCl\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e647\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e---\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e---\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eS-H\u0026middot;\u0026middot;\u0026middot;O\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eO\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e629\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e---\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003e---\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\n\u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n\u003cp\u003eLarge frequency shifts were obtained for the vibrational frequencies of several complexes. The largest changes occur for the O\u003csub\u003e3\u003c/sub\u003e dimer, with red shifts up to 51 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and blue shifts up to 25 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (for the antisymmetric stretching band). Larger frequency shifts are also seen for the O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e (+\u0026thinsp;12 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), O\u003csub\u003e3\u003c/sub\u003e-HCN (+\u0026thinsp;10 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO (-9 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and O\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO (+\u0026thinsp;8 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) complexes.\u003c/p\u003e\n\u003cp\u003eAt lower levels of basis set the C\u003csub\u003e1\u003c/sub\u003e structure of the O\u003csub\u003e3\u003c/sub\u003e-O\u003csub\u003e3\u003c/sub\u003e complex is calculated to be more stable than the C\u003csub\u003ei\u003c/sub\u003e structure. However, at the highest level (AVQZ) the dissociation energies of the C\u003csub\u003e1\u003c/sub\u003e and C\u003csub\u003ei\u003c/sub\u003e isomers are very close (559 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for C\u003csub\u003e1\u003c/sub\u003e, 556 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for C\u003csub\u003ei\u003c/sub\u003e ), despite significant differences in structure, such as shorter O-O distances in the C\u003csub\u003e1\u003c/sub\u003e isomer. Based on these results, it cannot be decided which structure is more stable. Extrapolation of dissociation energies to the complete basis set favor C\u003csub\u003ei\u003c/sub\u003e.\u003c/p\u003e"},{"header":"Summary","content":"\u003cp\u003eHigh-level theoretical methods were applied to obtain stable structures and properties for complexes of ozone with selected triatomic molecules, as well as with ammonia and methane. The largest dissociation energy was obtained for the hydrogen bonded O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e complex, larger than for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO. Large dissociation energies were obtained also for complexes of ozone with SO\u003csub\u003e2\u003c/sub\u003e, N\u003csub\u003e2\u003c/sub\u003eO, HCN and CO\u003csub\u003e2\u003c/sub\u003e. Hydrogen bonding with O\u003csub\u003e3\u003c/sub\u003e is compared to hydrogen bonding with O\u003csub\u003e2\u003c/sub\u003e. Dissociation energies for complexes with O\u003csub\u003e3\u003c/sub\u003e are two to four times larger than for complexes with O\u003csub\u003e2\u003c/sub\u003e. C\u003csub\u003e1\u003c/sub\u003e and C\u003csub\u003ei\u003c/sub\u003e structures of the ozone dimer have nearly the same dissociation energies. Calculated shifts in vibrational frequencies are large for the ozone dimer, especially for the antisymmetric stretching band of ozone.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eProvision of adequate computing facilities by the Digital Research Alliance of Canada is much appreciated. Thanks to Prof. S. D. Peyerimhoff for reading the manuscript and commenting on it.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contribution\u003c/strong\u003e All work was done by the author.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e No funding was received for this work.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability\u003c/strong\u003e \u003cstrong\u003eof data and material\u003c/strong\u003e All data are available upon request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCode availability\u003c/strong\u003e No new code was used in this work.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest\u003c/strong\u003e The author declares no competing interests.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eGrein F (2022) Ab initio studies on complexes of ozone with diatomic molecules, Structural Chemistry. 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Comp Theor Chem 1182:112834. https://doi.org/10.1016/j.comptc.2020.112834\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"O3-H2O, O3-H2S, O3-HCN, O3-NH3, O3-CH4, O3-CO2, O3-O3, O3-SO2, O3-N2O, O3-NO2 complexes, Coupled cluster calculations, Structures and dissociation energies, Vibrational frequencies, Hydrogen bonding","lastPublishedDoi":"10.21203/rs.3.rs-2202310/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-2202310/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eUsing coupled cluster methods with quadruple-zeta basis sets stable structures were found for complexes of ozone with common triatomic molecules as well as with ammonia and methane. The largest dissociation energy of 917 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was obtained for the hydrogen bonded O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e complex, exceeding the value for O\u003csub\u003e3\u003c/sub\u003e-H\u003csub\u003e2\u003c/sub\u003eO (787 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). The high dissociation energy of the O\u003csub\u003e3\u003c/sub\u003e-NH\u003csub\u003e3\u003c/sub\u003e complex is seen as an exception to the expected sequence of stabilities. Large dissociation energies were obtained also for O\u003csub\u003e3\u003c/sub\u003e-SO\u003csub\u003e2\u003c/sub\u003e (717 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), O\u003csub\u003e3\u003c/sub\u003e-N\u003csub\u003e2\u003c/sub\u003eO (688 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), O\u003csub\u003e3\u003c/sub\u003e-HCN (659 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and O\u003csub\u003e3\u003c/sub\u003e-CO\u003csub\u003e2\u003c/sub\u003e (652 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e). Dissociation energies for the C\u003csub\u003e1\u003c/sub\u003e structure (559 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and C\u003csub\u003ei\u003c/sub\u003e structure (556 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) of the ozone dimer are nearly identical despite pronounced differences in geometries. Hydrogen bonding of HF, H\u003csub\u003e2\u003c/sub\u003eO, NH\u003csub\u003e3\u003c/sub\u003e and CH\u003csub\u003e4\u003c/sub\u003e with ozone is contrasted to hydrogen bonding with the oxygen molecule. Large shifts in vibrational frequencies were found for the ozone dimer, with a red shift of 51 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and a blue shift of 25 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e for the antisymmetric stretching band of ozone. Larger frequency shifts are also seen for complexes of ozone with NH\u003csub\u003e3\u003c/sub\u003e, HCN, H\u003csub\u003e2\u003c/sub\u003eO and N\u003csub\u003e2\u003c/sub\u003eO.\u003c/p\u003e","manuscriptTitle":"Ab initio studies on complexes of ozone with triatomic and larger molecules. 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