Screening the effects of additional donors, numbers and positions of π-spacers on perylene- based sensitizers in dye-sensitized solar cell applications

Screening the effects of additional donors, numbers and positions of π-spacers on perylene- based sensitizers in dye-sensitized solar cell applications | 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 Screening the effects of additional donors, numbers and positions of π-spacers on perylene- based sensitizers in dye-sensitized solar cell applications D. Nicksonsebastin, P. Pounraj, E. Isac Paulraj, N. Mani, M. Prasath This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-2603551/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 09 Apr, 2024 Read the published version in Chemical Papers → Version 1 posted You are reading this latest preprint version Abstract The novel sensitizers are framed by perylene as donor with diphehylamine as auxiliary donor, thiophene and cyanovinyl as π-spacers and cyano acrylic acid as an acceptor unit. The optimised structure for the designed sensitizers was determined utilizing density functional theory, and the electronic structure was determined utilizing time-dependent density functional theory through the B3LYP/6-311G (d, p) basis set in the gas phase and Dimethylformamide (DMF) phase. The frontier molecular orbital results have significantly lower HOMO-LUMO energy gap values for better electron injection and electron regeneration. All designed sensitizers have absorption spectra values in the range of visible to near IR region. In the present work, the position and number of π-spacers reduces the HOMO-LUMO gap, the redshift of the absorption spectrum, and increases the high light harvesting efficiency. The findings reveal that the number of π-spacers improves the power conversion efficiency (PCE) of the solar cells. Diphenylamine perylene LHE DFT Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction The dye-sensitized solar cell (DSSC) was first introduced by O'Regan and Gratzel in 1991[ 1 ] and has a comprehensive mechanism. The photosensitizer absorbs the photon from solar radiation and injects the electron into the photo anode, such as TiO2, ZnO, etc., is the mechanism of the DSSC [ 2 ] and generates electric current in the circuit. The photo sensitizers are categorised into two types: metal sensitizers and metal-free organic sensitizers. The metal sensitizers like Ru complex and zinc phoperynin achieved a higher photon to current conversion efficiency (PCE) of > 11% [ 3 ]. In comparison to metal-free organic sensitizers, metal sensitizers have some drawbacks, such as high cost, environmental risk, and challenging purification. [ 4 ]. The metal-free organic sensitizers have received the most attention in DSSC due to their lower cost, modification of structure, and ease of fabrication [ 5 ]. The metal-free organic sensitizers achieved a higher PCE of 14.5% with the silyl anchor group [ 6 ]. The D-π-A structure of the sensitizers has the donor, π-spacers and acceptor units, which are broadly used to design dye sensitizers [ 7 , 8 ]. The D-π-A structured sensitizers were easily modified by the numbering and positions of the donors, π-spacers and acceptor units. The sensitizers has donor groups such as triphenylamine [ 9 ], perylene [ 10 ], carbazole [ 11 ], indoline [ 12 ], and coumarin [ 13 ]. The sensitizers possess aromatic hydrocarbons and delocalization properties which helps in electron donate nature. The π-spacers such as thiophene, cyanovinyl and thionothiophene are commonly used for photosensitizers [ 14 , 15 ], and their major role in the optical properties is to reduce the HOMO-LUMO energy gap of the sensitizers. The computational calculations were used to analyse the sensitizers in the theoretical method, which helps to develop highly efficient sensitizers without waste of time and cost [ 16 , 17 ]. In the theoretical method, DFT and TD-DFT theory functions were used to analyse the optical properties, optimised geometry, and electronic properties [ 18 ]. In the current work, perylene donor-based sensitizers were combined with thiophene and cyanovinyl as π-spacers. Perylene is an aromatic hydrocarbon that is used as a donor due to its planar structure and electron delocalization properties [ 19 ]. Thiophene and cyanovinyl are employed as π-spacers because of their high electron transfer nature. In diphenylamine, the additional donor for the donor part has two aromatic rings linked with nitrogen, which helps to improve the donating ability of the donor part [ 20 ]. Cyanoacryic acid is used as an acceptor group. In previous work, it was reported that the combination of π-spacers configurations combined with perylene donor [ 21 ]. This work focuses on the effects of numbering and positions of the π-spacers and the presence of additional donors for the donor part. Intramolecular charge transfer and electronic properties were analysed through coplanarity, frontier molecular orbital, natural bonding orbital, electron injection, and electron regeneration. The optical properties of the sensitizers were analysed by absorption maximum, light harvesting efficiency, and molar extension coefficient studies. Computational Details The entire set of computational calculations are calculated using the Gaussian 09w package and Gauss View 5.0 software [ 22 , 23 ]. The optimization of the chosen sensitizers were done by using Density Functional Theory (DFT) through the Becke's three-parameter hybrid functional of Lee-Yang Parr (B3LYP)/6-311G(d,p) basis set in the gas and DMF phase [ 24 , 25 ]. Utilising, the DFT calculations the HOMO-LUMO and dipole moment were used to describe the intramolecular charge transfer. The absorption spectrum and vertical excitation energy are determined by the polarizable continuum model (PCM) and investigated by Time Dependent-Density Functional Theory with CAM-B3LYP/6-311G(d,p) basis set in gas and DMF phases. The absorption maximum, vertical excitation energy, and oscillator strength can be predicted using TD-DFT functions. The excitation properties of the sensitizers were analysed by using the Gauss sum 3.0 program [ 26 ]. Results And Discussion Structure of the sensitizers The diphenylamine functionalized perylene donor is linked with cyanoacrylic acid through different numbers and positions of thiophene and cyanovinyl groups. The π-spacers are positioned into the six configurations. The configuration of the designed sensitizers listed in Table 1 , and the structural arrangement of sensitizers are, Table 1 Structural arrangement of DPP sensitizers Dyes Configurations Combinations of Donor-π-Acceptor DPP-1 Configuration − 1 D-P-CA DPP-2 Configuration − 2 D-P-C-T-CA DPP-3 Configuration − 3 D-P-T-C-CA DPP-4 Configuration − 4 D-P-C-T-C-T-CA DPP-5 Configuration − 5 D-P-C-T-T-C-CA DPP-6 Configuration − 6 D-P-T-T-C-C-CA D-Diphenylamine, P-Perylene, T-Thiophene, C-Cyanovinyl,CA-Cyanoacrylicacid Configuration 1: D-P-CA Configuration 2: D-P-C-T-CA Configuration 3: D-P-T-C-CA Configuration 4: D-P-C-T-C-T-CA Configuration 5: D-P-C-T-T-C-CA Configuration 6: D-P-T-T-C-C-CA The six configurations include models with and without π-spacers. Configuration 1 has only donor and acceptor parts. In configurations 2 and 3, the mono thiophene and cyanovinyl as a π-spacers and their positions were changed. Then configurations 4,5 and 6 have the double pair of thiophene and cyanovinyl groups which have different positions were analysed. The chemical structure of the sensitizers is depicted in Fig. 1 and geometrical structure of the sensitizers is depicted in Fig. 2 . Nbo Analysis The charge population of the sensitizer is predicted using natural bond orbital analysis, which demonstrates that intramolecular charge transfer from the donor to acceptor happens through π-spacers [ 27 – 32 ]. The total charge population of the donor part is indicated as q D and the positive value of q D represents that the donor part has more electrons to donate to the acceptor. The q A represents the charge population of the acceptor part, and the charge population of the π-spacer part is represented as q π . The negative q A value indicates that the acceptor has accepted an electron from the donor through π-spacer. The q π values are negative, the π-spacers act as acceptor units, and positive q π values indicate the π-spacers act as donor units. The q D−A represents the charge separation between the donor part to acceptor part. The positive q D−A value of the sensitizers has the best charge separation between the donor and acceptor parts, and values are listed in Table 2 . The DPP-2 has the highest q D−A values compared to the other sensitizers. DPP-1 has a q D−A value of 0.24167. The addition of π-spacers in DPP-2 increases the q D−A value, and changing the position of the π-spacers decreases the q D−A value in DPP-3. Then an increased number of π-spacer units decreases the q D−A value in DPP-4 compared to DPP-2. The higher positive value of q D−A value of DPP-2 is the better candidate for DSSC applications. Table 2 NBO analysis of DPP group of sensitizers. Dye q D q π q A q D−A DPP-1 0.1208 - -0.1208 0.2416 DPP-2 0.1230 0.0264 -0.1494 0.2724 DPP-3 0.0548 0.0394 -0.0942 0.1490 DPP-4 0.1190 0.0269 -0.1459 0.2649 DPP-5 0.1010 -0.0078 -0.0932 0.1942 DPP-6 0.0312 0.0490 -0.0801 0.1113 Frontier Molecular Orbitals The charge distribution of the donor to acceptor is influenced by frontier molecular orbital analysis. The photoexcitation process of the solar cell, involves the injection of electrons into the semiconductor diode [ 33 ]. The HOMO, LUMO, and HOMO-LUMO energy gap are determined by the charge separation process. Figure 3 depicts the charge distribution of the developed sensitizers. In HOMO, the density of the electron is delocalized into donor and π-spacer units. In LUMO, the density of electrons is delocalized into π-spacer and acceptor parts. The charge separation of the HOMO-LUMO improves the ICT of the solar cell. The examined sensitizers' HOMO and LUMO values, as well as the HOMO-LUMO energy gap, are given in Table 3 and depicted in Fig. 4 . The charge separation that took place during the photoexcitation procedure, the HOMO-LUMO energy gap values is minimized. The HOMO is below the redox electrolyte and the LUMO is above the CB of the TiO 2 semiconductor, according to the energy level diagram [ 34 ]. A Polarizable continuum model is used to optimize the studied sensitizer in the DMF phase. The energy gap of the sensitizers is reduced compared to the gas phase because of solvent polarisation. The energy levels are stabilised by solvent polarisation, which also causes a reduction in the energy gap. At 2.303 eV, DPP-1 has a larger band gap. Inclusion of π-spacers reduces the energy gap in DPP-2 compared to DPP-1. The positions of the π-spacers were changed and electron withdrawing (CN) groups lie near to the acceptor, which helps to decrease the energy gap of the sensitizers. Similarly, the configurations 4,5 and 6 have the number of π-spacers increases and the π-spacers positions were changed, which it is helps to reducing the energy gap. As a result, the energy gap of the sensitizers is affected by the increasing number and varied positions of π-spacers, and electron withdrawing groups close to the acceptor group. According to the aforementioned data, DPP-6 is ideal for DSSC applications since it has the lowest energy gap value when compared to other proposed sensitizers. Table 3 HOMO-LUMO values of DPP group of sensitizers in Gas and DMF phase . Dyes Gas phase (eV) E H−L DMF phase (eV) E H−L HOMO LUMO HOMO LUMO DPP-1 -5.2956 -2.9922 2.3035 -5.3174 -3.1092 2.2082 DPP-2 -5.2592 -3.3130 1.9462 -5.2785 -3.3563 1.9222 DPP-3 -5.2472 -3.3253 1.9220 -5.2554 -3.3647 1.8907 DPP-4 -5.2679 -3.5182 1.7497 -5.2660 -3.5032 1.7628 DPP-5 -5.3027 -3.5707 1.7320 -5.2559 -3.5261 1.7298 DPP-6 -5.2853 -3.7059 1.5794 -5.2312 -3.6698 1.5614 Optical Properties The absorption spectrum of the D-π-A structured sensitizers is in the range of visible to near IR. Maximum absorption and oscillator strength are critical for ICT because they improve absorption during the photoexcitation process [ 3 , 24 ]. The CAM-B3LYP/6-311G(d,p) basis set in gas and DMF phase is used in TD-DFT calculations to determine the absorption maximum, oscillator strength, and vertical excitation energy. Figure 5 depicts the sensitizers' absorption spectra. Table 4 lists the molar extinction coefficient (ε) and the absorption maximum (λ max ), whereas Table 5 lists the oscillator strength (f) and transition assignment. From Fig. 5 and Table 4 , It can be seen that the absorption maximum of DPP-1 is 470nm. In addition of π-spacers, the λ max values are red shifted by 53 nm, whereas the position of π-spacers is changed λ max is blue shifted by 34 nm. Similarly, the configurations 4,5 and 6 the number of π-spacers have been increased, induced the redshift of the spectrum, and changed the position of the π-spacers, induced the blueshift of the spectrum. Therefore, the number of π-spacers and position of π-spacers influence the absorption spectrum. The absorption maximum of the designed sensitizers is calculated by the DMF phase. The λ max is increased compared to the gas phase because of the solvent effect. Whereas the redshift and blueshift of the absorption maximum are similar to that of the gas phase. The molar extension coefficient (ε) is another important factor in absorbing the photons from sunlights to inject into the semiconductor conduction band. The ε values of DPP sensitizers are depicted in Table 4 . The ε values are in the range of 5.116 x 10 4 to 16.603 x 10 4 in the gas phase. When compared to the other configurations, configuration 6 has the highest value. In the DMF phase, all configurations have a higher value of ε compared to the gas phase due to the solvent effect. The higher value of ε for configuration 6 shows it as a more efficient sensitizer compared to other configurations. Light harvesting efficiency (LHE) is an important parameter to enhance the short circuit current (J sc ). The higher value of LHE indicates that the efficiency of the solar cell will be enhanced. The LHE value of the sensitizers is calculated by using the equation in the literature [ 35 ]. The LHE values of the designed sensitizers are summarized in Table 5 . From Table 5 , the LHE value of the DPP group of sensitizers is 0.7940 to 0.9948. The DPP-1 has the lower value of LHE. The number of π-spacers is increased, allowing the LHE to be increased. The electron withdrawing (CN) group lying near to the acceptor group enhances the LHE value. The above results reveal that the greater number of π-spacers and position of the π-spacers affect the absorption maximum, ε and LHE. As a result of its higher ε and LHE values, the DPP-6 is a more proficient candidate for DSSC applications. Table 5 Oscillator strength (f), Light harvesting efficiency of the DPP group of sensitizers. Dye f LHE TRANSITION ASSIGNMENT Major Minor DPP − 1 0.6862 0.7940 H->L (86%) H-2->L (10%) DPP − 2 1.1993 0.9368 H->L (73%) H-2->L (14%), H->L + 1 (7%) DPP − 3 1.1288 0.9257 H->L (65%), H-2->L (15%) H->L + 1 (12%), H-3->L (4%) DPP − 4 1.8911 0.9872 H->L (57%), H-2->L (19%) H->L + 1 (13%), H-3->L (4%) DPP − 5 2.2295 0.9941 H->L (46%), H-2->L (20%) H->L + 1 (19%), H-3->L (8%) DPP − 6 2.2875 0.9948 H->L (37%), H-3->L (25%) H-2->L (24%), H->L + 1 (9%) Electrochemical Properties Electron injection (ϕ inj ) is the process of injection of electrons into the CB of the TiO 2 from LUMO during the photoexcitation process. The electron injection is determined by the thermodynamic driving force (ΔG inject ). ΔG inject is calculated from the oxidation potential, vertical excitation energy of the sensitizers and reduction potential of the semiconductor. ΔG inject of the sensitizers is determined from the equation [ 9 ], $${{\Delta }G}_{inject }=OPES - {E}_{CB}^{SC}$$ 1 ………………………….. Where, OPES is the oxidation potential of the sensitizer in excited state \({E}_{CB}^{SC}\) is reduction potential of the semiconductor conduction band. $$OPES= RPGS- {\lambda }_{max}$$ 2 ………………………….. Where, RPGS is the reduction potential in ground state λ max is the vertical excitation energy of the sensitizers. Electron regeneration is determined by the following equation [ 36 ], ΔG reg = RPGS – E redox ………………………….. (3) Where, E redox is the oxidation potential of the redox electrolyte. The electron injection and electron regeneration of the sensitizers are listed in Table 6 . All the designed sensitizers have a negative value of ΔG inject and a positive value of ΔG reg , which means they possess the position of LUMO is above the conduction band of the semiconductors and the position of the HOMO is below the redox electrolyte. The lower negative value of ΔG inject and the lower positive ΔG reg indicate that the DSSC is more efficient. The electron injection of the designed sensitizers is in the range of -0.970 to -1.344. Configuration 4 has the lower negative value of ΔG inject and it has the greater number of π-spacers units. Configuration 3, on the other hand, has a lower positive value of ΔG reg . The above results reveal that the DPP-4 has the lower negative value of ΔG inject and the DPP-3 has the lower positive value of ΔG reg value compared to other sensitizers. Table 6 Electron injection (ΔG inject ), electron regeneration (ΔG reg ) of the DPP group of sensitizers. Dyes E Ox λ max OPES ΔG inject ΔG reg DPP − 1 5.2956 2.6400 2.656 -1.344 0.496 DPP − 2 5.2592 2.3691 2.890 -1.110 0.459 DPP − 3 5.2472 2.5355 2.712 -1.288 0.447 DPP − 4 5.2679 2.2375 3.030 -0.970 0.468 DPP − 5 5.3027 2.3014 3.001 -0.999 0.503 DPP − 6 5.2853 2.4000 2.885 -1.115 0.485 Nlo Properties The NLO properties are determined by the electronic properties of the sensitizers. The higher values of dipole moment and polarizability generate the electron hole pair in the DSSC [ 37 ]. From Table 7 , the dipole moment value of DPP-1 is found to be 7.9521debye. Configuration 6 has the higher value of µ 18.5055 debye compared to the other configurations. One of the key criteria for greater polarizability is electron density. The polarizability values of the DPP sensitizers are increased in the order: DPP-1 < DPP-2 < DPP-3 < DPP-4 < DPP-5 < DPP-6. With configuration 1, which has the lower value of α and the inclusion of π-spacers in configuration 2, the value was increased due to the increased electron density of the sensitizers. Similarly, because of the increased number and changed positions of π-spacers, configurations 4,5 and 6 have higher values. The configuration 6 of the DPP sensitizers has a higher value of α compared to the other configurations. According to the aforementioned findings, configuration 6 has a greater dipole moment and polarizability value, which makes it a better fit for DSSC applications. Table 7 NLO properties of the DPP group of sensitizers. Dye Dipole moment Polarizability (au) x10 − 23 esu DPP − 1 7.9521 303.168 4.493 DPP − 2 4.6716 346.692 5.138 DPP − 3 11.7348 364.861 5.407 DPP − 4 8.9936 417.273 6.184 DPP − 5 16.5646 464.125 6.878 DPP − 6 18.5055 484.457 7.179 Conclusion DFT and TD-DFT functions in the B3LYP/6-311G(d,p) basis set are used to investigate six diphenylamine functionalized perylene-based sensitizer configurations. The NBO analysis reveals that configuration 2 has the higher positive value of q D−A and possesses better electron donating ability when compared with the other configurations. Frontier molecular orbital analysis and NLO properties results reveal that the numbering and changed positions of the π-spacers are influenced by the HOMO-LUMO energy gap, dipole moment, and polarizability values. The absorption spectrum analysis reveals that configuration 6 has the red shift of the absorption spectrum, a higher molar extension coefficient, and higher LHE values, so configuration 6 is the better candidate for DSSC applications. The electron injection and electron regeneration results reveal that configuration 4 and configuration 3 have the best ΔG inject and ΔG reg values compared to the other configurations. All the above discussion reveals that configuration 6 has the lower HOMO-LUMO energy gap, higher µ and α values, red shift of the absorption spectra, higher ε value and higher LHE values and it reveals that DPP-6 is the better candidate for DSSC applications. Declarations Author Contributions: 1) D.Nicksonsebastin conception or design of the work, acquisition, analysis, or interpretation of data, drafted the work or revised it critically for important intellectual content, approved the version to be published 2) P.Pounraj conception or design of the work, 3) E. Isac Paulraj acquisition, analysis, or interpretation of data 4) N.Mani drafted the work or revised it critically for important intellectual content 5) M.Prasath conception or design of the work acquisition, analysis, or interpretation of data drafted the work or revised it critically for important intellectual content approved the version to be published The first draft of the manuscript was written by D.Nicksonsebastin and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript The authors declare that no funds, grants, or other support were received during the preparation of this manuscript. 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Heliyon 6(8):e04641. https://doi.org/10.1016/j.heliyon.2020.e04641 Govindammal M, Prasath M, Selvapandiyan M (2021) Spectroscopic (FT-IR, FT-Raman) investigations, quantum chemical calculations, ADMET and molecular docking studies of phloretin with B-RAF inhibitor Chem Pap 75:3771–3785. https://doi.org/10.1007/s11696-021-01576-0 Govindammal M, Kannan S, Srinivasan P, Prasath M (2022) Quantum chemical calculations, spectroscopic studies and molecular docking investigations of the anti-cancer drug quercitrin with B-RAF inhibitor. Heliyon 8: e09539. https://doi.org/10.1016/j.heliyon.2022.e09539 Mohankumar V, Pounraj P, Pandian M S. et al. (2021) Role of π conjugation in n-hexylphenothiazine dyes for solar cell—a density functional theory approach. J Mol Model 27: 151. https://doi.org/10.1007/s00894-021-04769-2 Nicksonsebastin D, Pounraj P, Mani N. et al. (2022) Screening the influence of methoxy and anisyl groups to perylene based sensitizers for dye-sensitized solar cell applications: a computational approach. J Mol Model 28, 373. https://doi.org/10.1007/s00894-022-05363-w Gupta V D, Tathe A B, Padalkar V S, Umape, P G, Sekar N, (2013) Red emitting solid state fluorescent triphenylamine dyes: Synthesis, photo-physical property and DFT study. Dye. Pigment. 97:429-439. https://doi.org/10.1016/j.dyepig.2012.12.024 Mahmood A, Khan S UD, Rana U A. (2014) Theoretical designing of novel heterocyclic azo dyes for dye sensitized solar cells. J Comput Electron 13 , 1033–1041. https://doi.org/10.1007/s10825-014-0628-2 Mahmood A, Hussaintahir M, Irfan A, Khalid B, Al-Sehemi A G (2015) Computational Designing of Triphenylamine Dyes with Broad and Red-shifted Absorption Spectra for Dye-sensitized Solar Cells using Multi-Thiophene Rings in π-Spacer. Bull. Korean Chem. Soc. 36, 2615-2620. https://doi.org/10.1002/bkcs.10526 Bai Y, Zhang J, et al. (2011) Engineering Organic Sensitizers for Iodine-Free Dye-Sensitized Solar Cells: Red-Shifted Current Response Concomitant with Attenuated Charge Recombination. J Am Chem Soc 133:11442–11445. https://doi.org/10.1021/ja203708k Prakasam M, Anbarasan PM (2016) Second order hyperpolarizabilityof triphenylamine based organic sensitizers: a first principle theoretical study. RSC Adv 6:75242–75250. https:// doi. org/ 10.1039/ C6RA1 1200E Additional Declarations No competing interests reported. Cite Share Download PDF Status: Published Journal Publication published 09 Apr, 2024 Read the published version in Chemical Papers → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-2603551","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":179396257,"identity":"6cb547bf-00c4-46a3-aa3e-80917a07e5f8","order_by":0,"name":"D. Nicksonsebastin","email":"","orcid":"","institution":"Periyar University centre for Post Graduate and Research studies","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"D.","middleName":"","lastName":"Nicksonsebastin","suffix":""},{"id":179396258,"identity":"84e223a3-32c3-4a11-b489-ce6ccb1c1e77","order_by":1,"name":"P. Pounraj","email":"","orcid":"","institution":"The American College","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"P.","middleName":"","lastName":"Pounraj","suffix":""},{"id":179396259,"identity":"bdf9f05c-fc94-4563-a59e-ce4336d45190","order_by":2,"name":"E. Isac Paulraj","email":"","orcid":"","institution":"Loyala Institute of Technology","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"E.","middleName":"Isac","lastName":"Paulraj","suffix":""},{"id":179396260,"identity":"e42e48ed-4f01-4b66-8496-521c179bc01a","order_by":3,"name":"N. Mani","email":"","orcid":"","institution":"Periyar University centre for Post Graduate and Research studies","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"N.","middleName":"","lastName":"Mani","suffix":""},{"id":179396261,"identity":"8bdc5fb5-4c2c-4e00-9896-585d6f7a125f","order_by":4,"name":"M. Prasath","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAABCUlEQVRIiWNgGAWjYFADCeYDBxIqbIAsxsYDROngkWBLfPDhTBpISwOxWniMDWe2HAZz8GqRbz977HFFTZ28vXSDmTRvw3m7te2HgbbU2ETj0mJwJi/d8Myxw4Y9MgfSpHl33E7ediYRqOVYWm4DLi0MOWaSDWwHGHskEo5J8565nWx2AKiFseEwTi3y/W+AWv7V2fdIJLZJ87adSzY7/xC/FoYbQFsa25gTeySSmQ1nth2wM7tBwBaDG2/MDRv7Dif33EhjBAZycoLZDaAtCXj8It+fY/aw4VudbfuM/A/AqLSzNzuf/vDBhxob3A5jYGBD4SWCVSbgVo6pxR6/4lEwCkbBKBiJAACfe2gX+uO2UwAAAABJRU5ErkJggg==","orcid":"","institution":"Periyar University centre for Post Graduate and Research studies","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"M.","middleName":"","lastName":"Prasath","suffix":""}],"badges":[],"createdAt":"2023-02-19 05:59:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-2603551/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-2603551/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11696-024-03429-y","type":"published","date":"2024-04-09T05:07:51+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":33863599,"identity":"0218f2b6-c069-4f6b-931b-7a5ae0c572a3","added_by":"auto","created_at":"2023-03-06 23:30:03","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":275281,"visible":true,"origin":"","legend":"\u003cp\u003eThe chemical structure of the DPP sensitizers.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-2603551/v1/a78b2f5e0f5bb0bbfe9c271f.png"},{"id":33863598,"identity":"0d2ab56b-acf8-4835-9cd6-ba8e7332ba48","added_by":"auto","created_at":"2023-03-06 23:30:03","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":462656,"visible":true,"origin":"","legend":"\u003cp\u003eThe geometrical structure of the DPP sensitizers\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-2603551/v1/1b6f21abcd57c6c3bae32ccd.png"},{"id":33864266,"identity":"7b810a5b-113a-4402-95f9-9aceb28d880a","added_by":"auto","created_at":"2023-03-06 23:38:03","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":956616,"visible":true,"origin":"","legend":"\u003cp\u003eThe ground state density plot HOMO and LUMO of the DPP sensitizers\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-2603551/v1/55afbec96f89928ae4cc3d69.png"},{"id":33863600,"identity":"8660ed08-47d6-4783-83d0-f04d7efeddc2","added_by":"auto","created_at":"2023-03-06 23:30:03","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":145341,"visible":true,"origin":"","legend":"\u003cp\u003eThe HOMO-LUMO energy level of the DPP sensitizers in gas phase.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-2603551/v1/073723be60e1055dc170e0a3.png"},{"id":33863601,"identity":"7e27233b-d763-4eef-a5bc-5d92df8059d9","added_by":"auto","created_at":"2023-03-06 23:30:03","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":403548,"visible":true,"origin":"","legend":"\u003cp\u003eElectronic absorption spectra of DPP group sensitizers in gas phase.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-2603551/v1/ce2d4dcefa632e09fba1cfa6.png"},{"id":58849052,"identity":"f2254f84-a711-4b2c-8174-2695c494b828","added_by":"auto","created_at":"2024-06-22 05:23:57","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2885011,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-2603551/v1/dcc40af1-cd8d-43a3-82b3-0c9c364e8280.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"Screening the effects of additional donors, numbers and positions of π-spacers on perylene- based sensitizers in dye-sensitized solar cell applications","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe dye-sensitized solar cell (DSSC) was first introduced by O'Regan and Gratzel in 1991[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e] and has a comprehensive mechanism. The photosensitizer absorbs the photon from solar radiation and injects the electron into the photo anode, such as TiO2, ZnO, etc., is the mechanism of the DSSC [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e] and generates electric current in the circuit. The photo sensitizers are categorised into two types: metal sensitizers and metal-free organic sensitizers. The metal sensitizers like Ru complex and zinc phoperynin achieved a higher photon to current conversion efficiency (PCE) of \u0026gt;\u0026thinsp;11% [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. In comparison to metal-free organic sensitizers, metal sensitizers have some drawbacks, such as high cost, environmental risk, and challenging purification. [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. The metal-free organic sensitizers have received the most attention in DSSC due to their lower cost, modification of structure, and ease of fabrication [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. The metal-free organic sensitizers achieved a higher PCE of 14.5% with the silyl anchor group [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. The D-π-A structure of the sensitizers has the donor, π-spacers and acceptor units, which are broadly used to design dye sensitizers [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. The D-π-A structured sensitizers were easily modified by the numbering and positions of the donors, π-spacers and acceptor units. The sensitizers has donor groups such as triphenylamine [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e], perylene [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], carbazole [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e], indoline [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e], and coumarin [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. The sensitizers possess aromatic hydrocarbons and delocalization properties which helps in electron donate nature. The π-spacers such as thiophene, cyanovinyl and thionothiophene are commonly used for photosensitizers [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e], and their major role in the optical properties is to reduce the HOMO-LUMO energy gap of the sensitizers. The computational calculations were used to analyse the sensitizers in the theoretical method, which helps to develop highly efficient sensitizers without waste of time and cost [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. In the theoretical method, DFT and TD-DFT theory functions were used to analyse the optical properties, optimised geometry, and electronic properties [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. In the current work, perylene donor-based sensitizers were combined with thiophene and cyanovinyl as π-spacers. Perylene is an aromatic hydrocarbon that is used as a donor due to its planar structure and electron delocalization properties [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. Thiophene and cyanovinyl are employed as π-spacers because of their high electron transfer nature. In diphenylamine, the additional donor for the donor part has two aromatic rings linked with nitrogen, which helps to improve the donating ability of the donor part [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Cyanoacryic acid is used as an acceptor group. In previous work, it was reported that the combination of π-spacers configurations combined with perylene donor [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. This work focuses on the effects of numbering and positions of the π-spacers and the presence of additional donors for the donor part. Intramolecular charge transfer and electronic properties were analysed through coplanarity, frontier molecular orbital, natural bonding orbital, electron injection, and electron regeneration. The optical properties of the sensitizers were analysed by absorption maximum, light harvesting efficiency, and molar extension coefficient studies.\u003c/p\u003e"},{"header":"Computational Details","content":"\u003cp\u003eThe entire set of computational calculations are calculated using the Gaussian 09w package and Gauss View 5.0 software [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. The optimization of the chosen sensitizers were done by using Density Functional Theory (DFT) through the Becke's three-parameter hybrid functional of Lee-Yang Parr (B3LYP)/6-311G(d,p) basis set in the gas and DMF phase [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Utilising, the DFT calculations the HOMO-LUMO and dipole moment were used to describe the intramolecular charge transfer. The absorption spectrum and vertical excitation energy are determined by the polarizable continuum model (PCM) and investigated by Time Dependent-Density Functional Theory with CAM-B3LYP/6-311G(d,p) basis set in gas and DMF phases. The absorption maximum, vertical excitation energy, and oscillator strength can be predicted using TD-DFT functions. The excitation properties of the sensitizers were analysed by using the Gauss sum 3.0 program [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e].\u003c/p\u003e"},{"header":"Results And Discussion","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eStructure of the sensitizers\u003c/h2\u003e \u003cp\u003eThe diphenylamine functionalized perylene donor is linked with cyanoacrylic acid through different numbers and positions of thiophene and cyanovinyl groups. The π-spacers are positioned into the six configurations. The configuration of the designed sensitizers listed in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, and the structural arrangement of sensitizers are,\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eStructural arrangement of DPP sensitizers\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDyes\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eConfigurations\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCombinations of Donor-π-Acceptor\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eConfiguration \u0026minus;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eD-P-CA\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eConfiguration \u0026minus;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eD-P-C-T-CA\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eConfiguration \u0026minus;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eD-P-T-C-CA\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eConfiguration \u0026minus;\u0026thinsp;4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eD-P-C-T-C-T-CA\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eConfiguration \u0026minus;\u0026thinsp;5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eD-P-C-T-T-C-CA\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eConfiguration \u0026minus;\u0026thinsp;6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eD-P-T-T-C-C-CA\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003ctfoot\u003e \u003ctr\u003e\u003ctd colspan=\"3\"\u003eD-Diphenylamine, P-Perylene, T-Thiophene, C-Cyanovinyl,CA-Cyanoacrylicacid\u003c/td\u003e\u003c/tr\u003e \u003c/tfoot\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eConfiguration 1: D-P-CA\u003c/p\u003e \u003cp\u003eConfiguration 2: D-P-C-T-CA\u003c/p\u003e \u003cp\u003eConfiguration 3: D-P-T-C-CA\u003c/p\u003e \u003cp\u003eConfiguration 4: D-P-C-T-C-T-CA\u003c/p\u003e \u003cp\u003eConfiguration 5: D-P-C-T-T-C-CA\u003c/p\u003e \u003cp\u003eConfiguration 6: D-P-T-T-C-C-CA\u003c/p\u003e \u003cp\u003eThe six configurations include models with and without π-spacers. Configuration 1 has only donor and acceptor parts. In configurations 2 and 3, the mono thiophene and cyanovinyl as a π-spacers and their positions were changed. Then configurations 4,5 and 6 have the double pair of thiophene and cyanovinyl groups which have different positions were analysed. The chemical structure of the sensitizers is depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and geometrical structure of the sensitizers is depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eNbo Analysis\u003c/h3\u003e\n\u003cp\u003eThe charge population of the sensitizer is predicted using natural bond orbital analysis, which demonstrates that intramolecular charge transfer from the donor to acceptor happens through π-spacers [\u003cspan additionalcitationids=\"CR28 CR29 CR30 CR31\" citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. The total charge population of the donor part is indicated as q\u003csup\u003eD\u003c/sup\u003e and the positive value of q\u003csup\u003eD\u003c/sup\u003e represents that the donor part has more electrons to donate to the acceptor. The q\u003csup\u003eA\u003c/sup\u003e represents the charge population of the acceptor part, and the charge population of the π-spacer part is represented as q\u003csup\u003eπ\u003c/sup\u003e. The negative q\u003csup\u003eA\u003c/sup\u003e value indicates that the acceptor has accepted an electron from the donor through π-spacer. The q\u003csup\u003eπ\u003c/sup\u003e values are negative, the π-spacers act as acceptor units, and positive q\u003csup\u003eπ\u003c/sup\u003e values indicate the π-spacers act as donor units. The q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e represents the charge separation between the donor part to acceptor part. The positive q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e value of the sensitizers has the best charge separation between the donor and acceptor parts, and values are listed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The DPP-2 has the highest q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e values compared to the other sensitizers. DPP-1 has a q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e value of 0.24167. The addition of π-spacers in DPP-2 increases the q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e value, and changing the position of the π-spacers decreases the q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e value in DPP-3. Then an increased number of π-spacer units decreases the q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e value in DPP-4 compared to DPP-2. The higher positive value of q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e value of DPP-2 is the better candidate for DSSC applications.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eNBO analysis of DPP group of sensitizers.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"5\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDye\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eq\u003csup\u003eD\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eq\u003csup\u003eπ\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eq\u003csup\u003eA\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eq\u003csup\u003eD\u0026minus;A\u003c/sup\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.1208\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-0.1208\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.2416\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.1230\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.0264\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-0.1494\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.2724\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.0548\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.0394\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-0.0942\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.1490\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.1190\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.0269\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-0.1459\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.2649\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.1010\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-0.0078\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-0.0932\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.1942\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.0312\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.0490\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e-0.0801\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.1113\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e\n\u003ch3\u003eFrontier Molecular Orbitals\u003c/h3\u003e\n\u003cp\u003eThe charge distribution of the donor to acceptor is influenced by frontier molecular orbital analysis. The photoexcitation process of the solar cell, involves the injection of electrons into the semiconductor diode [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. The HOMO, LUMO, and HOMO-LUMO energy gap are determined by the charge separation process. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e depicts the charge distribution of the developed sensitizers. In HOMO, the density of the electron is delocalized into donor and π-spacer units. In LUMO, the density of electrons is delocalized into π-spacer and acceptor parts. The charge separation of the HOMO-LUMO improves the ICT of the solar cell. The examined sensitizers' HOMO and LUMO values, as well as the HOMO-LUMO energy gap, are given in Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e and depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The charge separation that took place during the photoexcitation procedure, the HOMO-LUMO energy gap values is minimized. The HOMO is below the redox electrolyte and the LUMO is above the CB of the TiO\u003csub\u003e2\u003c/sub\u003e semiconductor, according to the energy level diagram [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e]. A Polarizable continuum model is used to optimize the studied sensitizer in the DMF phase. The energy gap of the sensitizers is reduced compared to the gas phase because of solvent polarisation. The energy levels are stabilised by solvent polarisation, which also causes a reduction in the energy gap. At 2.303 eV, DPP-1 has a larger band gap. Inclusion of π-spacers reduces the energy gap in DPP-2 compared to DPP-1. The positions of the π-spacers were changed and electron withdrawing (CN) groups lie near to the acceptor, which helps to decrease the energy gap of the sensitizers. Similarly, the configurations 4,5 and 6 have the number of π-spacers increases and the π-spacers positions were changed, which it is helps to reducing the energy gap. As a result, the energy gap of the sensitizers is affected by the increasing number and varied positions of π-spacers, and electron withdrawing groups close to the acceptor group. According to the aforementioned data, DPP-6 is ideal for DSSC applications since it has the lowest energy gap value when compared to other proposed sensitizers.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eHOMO-LUMO values of DPP group of sensitizers in Gas and DMF phase .\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eDyes\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e \u003cp\u003eGas phase (eV)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eE\u003csub\u003eH\u0026minus;L\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c6\" namest=\"c5\"\u003e \u003cp\u003eDMF phase (eV)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eE\u003csub\u003eH\u0026minus;L\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eHOMO\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eLUMO\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eHOMO\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eLUMO\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-5.2956\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-2.9922\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.3035\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-5.3174\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-3.1092\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e2.2082\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-5.2592\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-3.3130\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.9462\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-5.2785\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-3.3563\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.9222\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-5.2472\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-3.3253\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.9220\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-5.2554\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-3.3647\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.8907\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-5.2679\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-3.5182\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.7497\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-5.2660\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-3.5032\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.7628\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-5.3027\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-3.5707\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.7320\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-5.2559\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-3.5261\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.7298\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP-6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e-5.2853\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e-3.7059\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.5794\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-5.2312\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e-3.6698\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e \u003cp\u003e1.5614\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e\n\u003ch3\u003eOptical Properties\u003c/h3\u003e\n\u003cp\u003eThe absorption spectrum of the D-\u0026pi;-A structured sensitizers is in the range of visible to near IR. Maximum absorption and oscillator strength are critical for ICT because they improve absorption during the photoexcitation process [\u003cspan class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan class=\"CitationRef\"\u003e24\u003c/span\u003e]. The CAM-B3LYP/6-311G(d,p) basis set in gas and DMF phase is used in TD-DFT calculations to determine the absorption maximum, oscillator strength, and vertical excitation energy. Figure \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e depicts the sensitizers\u0026apos; absorption spectra. Table \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e lists the molar extinction coefficient (\u0026epsilon;) and the absorption maximum (\u0026lambda;\u003csub\u003emax\u003c/sub\u003e), whereas Table \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e lists the oscillator strength (f) and transition assignment. From Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e and Table \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e, It can be seen that the absorption maximum of DPP-1 is 470nm. In addition of \u0026pi;-spacers, the \u0026lambda;\u003csub\u003emax\u003c/sub\u003e values are red shifted by 53 nm, whereas the position of \u0026pi;-spacers is changed \u0026lambda;\u003csub\u003emax\u003c/sub\u003e is blue shifted by 34 nm. Similarly, the configurations 4,5 and 6 the number of \u0026pi;-spacers have been increased, induced the redshift of the spectrum, and changed the position of the \u0026pi;-spacers, induced the blueshift of the spectrum. Therefore, the number of \u0026pi;-spacers and position of \u0026pi;-spacers influence the absorption spectrum. The absorption maximum of the designed sensitizers is calculated by the DMF phase. The \u0026lambda;\u003csub\u003emax\u003c/sub\u003e is increased compared to the gas phase because of the solvent effect. Whereas the redshift and blueshift of the absorption maximum are similar to that of the gas phase. The molar extension coefficient (\u0026epsilon;) is another important factor in absorbing the photons from sunlights to inject into the semiconductor conduction band. The \u0026epsilon; values of DPP sensitizers are depicted in Table \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e. The \u0026epsilon; values are in the range of 5.116 x 10\u003csup\u003e4\u003c/sup\u003e to 16.603 x 10\u003csup\u003e4\u003c/sup\u003e in the gas phase. When compared to the other configurations, configuration 6 has the highest value. In the DMF phase, all configurations have a higher value of \u0026epsilon; compared to the gas phase due to the solvent effect. The higher value of \u0026epsilon; for configuration 6 shows it as a more efficient sensitizer compared to other configurations. Light harvesting efficiency (LHE) is an important parameter to enhance the short circuit current (J\u003csub\u003esc\u003c/sub\u003e). The higher value of LHE indicates that the efficiency of the solar cell will be enhanced. The LHE value of the sensitizers is calculated by using the equation in the literature [\u003cspan class=\"CitationRef\"\u003e35\u003c/span\u003e]. The LHE values of the designed sensitizers are summarized in Table \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e. From Table \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e, the LHE value of the DPP group of sensitizers is 0.7940 to 0.9948. The DPP-1 has the lower value of LHE. The number of \u0026pi;-spacers is increased, allowing the LHE to be increased. The electron withdrawing (CN) group lying near to the acceptor group enhances the LHE value. The above results reveal that the greater number of \u0026pi;-spacers and position of the \u0026pi;-spacers affect the absorption maximum, \u0026epsilon; and LHE. As a result of its higher \u0026epsilon; and LHE values, the DPP-6 is a more proficient candidate for DSSC applications.\u003c/p\u003e\n\u003cp\u003e\u003cimg 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AgAAoBYElgAAAKgFgSUAAABqQWAJAACAWhBYAgAAoBYElgAAAKgFgSUAAABqQWAJAACAWhBYAgAAoBb/2XUBGo3GrosAAADwJiildl2EhXYeWO77BgIAAMBqGAoHAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAPijXdaXRaEij0RDXdXddHLwDBJYAAHxAQRCI67qilBKllKRpKtPpdNfFwhu38wekAwCA7Ts8PCy85w+WoA5csQQA4APq9XpycnKSD4VztRJ1ILAEsFGj0UgajYbEcbzrogAwuK4rDw8P+VB4q9XadZHwDhBYAtioP3/+iFJKrq+vd10UAIY0TQvvR6ORjEajHZUG70VDkVQBYAtGo5Gcn59Ls9ncdVEAiEiWZeI4Tv7ecRyZzWY7LBHeAwJLAFsxnU7l6elJOp3OrosCANgQhsIBbM3j4+OuiwAA2CCuWALYina7LSIit7e3Oy4JAGBTuGIJYOOyLJPJZEJ+JQC8cwSWADbux48f4nmenJyc8Kw8AHjHCCwBbNx4PJbBYCBHR0fy69cvEXm+itloNPLnXE6nU3FdNx8y19PNeY1GQ4Ig4LmYALCnCCwBbNRoNBLHcaTVakmz2ZT7+3sREfn586f4vi/39/eSJIkcHx/L3d1d/rlerydJkoiIyNPTU/4YlMvLS0mShLvLAdQiy7L8hBavR2AJYGOyLJN+vy/D4TCfdnFxIY1GQ/78+SMiIoPBQEREfN+XZrOZB5BxHMtwOJQoivLPJkkijUZji78AwFsxnU4r/zSlPQJiCoJgW0X8EAgsAWxMs9kUpVTh6mKn0xGllFxeXi787MPDw9wyT09PEoZhPpwOACLPgePx8XHpvDiO5erqKv/TlcfHx5JlWT7v4uJim0V99/6z6wIA+Jim06mMx+N8+DtNU8myTNI0lSAI5PDwsPBXQfSfhLy4uJButyt//vxZGpwC+Bh6vZ6cn58X+gxtMBgURk3CMJQfP37I5eWlPDw8yPfv3/mTszXiiiWAnWi1WqKUktlsJrPZTJRScnt7m1/N7PV6+RUG83G7q17xBPA+mMPY+u+ZVw1r2/TJ6tHRUT7t4OBA7u7uZDQayXg8FsdxZDKZ8HfSa8ID0gEAwF6L41i63a4kSSKfPn0Sx3HEDl/03z5PkkRarZaIPI+MHB8fF5a1p2VZJkEQ8McbasJQOAAA2GudTkceHx/zPEquie0vhsIBAMDe6/V64nneWp/59OmTiEh+s47I802AZi5ms9nkamWNCCy3LI7jPDek7GXu/AAA4FkQBHJxcSGe54nruit9ptlsiuM48vfv33za4+OjnJ2dbaqYHx6B5ZbpGw8cx5Eoigo3JziOI47jkEAMAIBhNBrJycmJdDqd/Oriqg81Hw6H+V3h+tm6379/31hZPzoCyz0ym83E8zzp9/v8PWUAAOR5pK/f70u32xWR5yAzTVOZTCb5lcs4jvPh7ePj48IFmk6nI6enp9JoNPKbe5rN5vZ/yAdBYLln9CNUbm5u8r+NbD5Sod1uF/5OsvnYBf4kFQDgvdEjffqGHfNRZPovdZnLKKWk1+sV1mF+Rt8xjs0gsNwz+iwqy7L8CmYYhnlDGAwGEkWRdDqd/IxMNxaewwUAAHZKYSccx1FRFJXOExHleZ5SSqkkSZSIqDRNlVJK+b5fWIeIFF76cx+NvR148eLFixev9/jadzzHcs/ou8JPT09F5Pmvk3ieJz9//py7tC8i+dXLj07xTDMAAHaOofA9EwSBiIicn5/n0y4uLqTf70scx/L169fC8o+Pj6WfBwAA2DYCyz3iuq5MJhOJoqhwx1qn0xHHcWQwGBSSjr99+1a4g3w6ncrh4eHWyw0AACDC3wrfOv33TqtUVYe+KcceDg+CQMbjsYiIeJ7HXw8AAAA7Q2D5RoxGIzk/P+fZWwAAYG8xFP5G3N/fE1QCAIC9RmC5x8yHnzPEDQAA9h1D4QAAAKgFVywBAABQCwJLAAAA1ILAEthz0+lUGo1G/leZ8H5Qt29fHMfSaDR2XQy8Qrvd5o+L1IjAEliBvolKv0T+PVt0k7Isk+Pj441/z3ti15X5MutMBwSNRkPa7Xbl+nTwt8prnQCRuq3PrtrndDpd+FzijyoIgso24rpuYdlV24/ruiu1wXXrPQgCmUwmL/qdKEdgCSyggwrf90Uplb8ajYZcXV1t/PubzaYkSbLx73lPlFIShqF4nleoszAMpd/v5we2TqeT/0GCyWSS/wUr283NjYiIJEmSr8txHImiaG7966BuX2/X7bPVakkURRv/nrfm8vJS0jQVEZE0TfN6SdNU0jSVRqORtzellPi+LyIiP378KF3fdDqVNE0L9VzWxvV3rltWz/Ne+EtRhsASWOD4+Fh835fLy8vCdKXU3Jk39luv15MoiiRN08Kwl+/74nmeDIfDuc+scwWy1+vxrNkto32+Lc1mMz+ZM6/WHx4eShiGMh6PS9vccDjMg89l67f/Oh22j8ASqBDHsYiIfP/+vXS++WxRe7jUHI5pt9v5GXpVHk8QBNJutwvPLi27gqbnmeuxh510x5xlWT70NJ1O898jUhxWMqe/d51ORzzPy/8MqnZxcVF61fLnz5+V9W9aNJQ+Go3Edd3C0HvZNq+rbvX+9pJhwbdk39qnrpOq9ZvD9GaZ2u22xHFcWN97b5/6Kq/5287Pz0Vk/qpllmVyenq6dJ1BEFSeCOq6MfeDsjZr1q9e10v2HbOtf8gTHAWglO/7atUm4nmeiqJIKaVUGIb556IoUmEY5st4njf3Wb28iOTLmt+dJEk+33yvlFJpmhbK6DiO8n0//740TfNldPkcx1FpmublE5H8/XsRhmHptlbq37bVv1lvL3PbaXodIqKSJMmnO46T14mIVH6X3r4ikq9b13eaprXXred5eTn1usxyvyf70j51HTuOk7/X/0+SJP+/UqqwDnMZs57eS/vU+2ZZ2fVv1tsiDEOVpmmhbjTf91Wapsr3/UL7NOtFv6q2k7mMWTaz7u335v/X2XeiKCqUs6xfee8ILIEKVQcuPV2/7AO3GRzoA8Mq32Ue1HTHlyRJvj7daS7qsM3O1/O8uQ7NDGTMl+4434uXBJb2QTyKorxuywJLc5stOnCEYVgILvT69Prrqlv9WfulD37vzb60T3sd5vptZsDiOM5c3byn9vmSwFIpNbfP6v28LLA068RcR1VZzH3BrFO7PdnfZZdbqep9Rwep5stu/+8dQ+FAhcPDQxGRuSEvOzG91Wrl89rtdiF3SA+9LhreLrNurp4e6jGHeC8vL2U8HpcOxygj4V0pJZ1OZ63ve8uyLBPHcea2cafTEcdx8qG4h4eHQt0uYuf4LeM4zsrLrlu35s0SSql3m3P2ltqnHk417z6+vr6Wfr9fOiz73tvn09OTiIh8+fJlbp6+yU7keWh6lVQUkfVznPX+s6p19p0wDAv1N5vN1vqut47AEqigc34uLi6WLqtz4QaDwdydvre3t/mdj8fHx2vdEPLp06elyzQaDTk7OyvcXSnyL1Fe/d/dkubByyyDnaP3nsVxLJPJRL59+1Y6fzgcyng8ljiO5eTkZKNl+fz589JlXlK3f//+zf+fZdm7zbN8C+1TnxQMh0NRShXuPm61Wnn9TSaTQo7ee2+f3W5XHMcpPXHTJ0Kj0Uj+/Pmz0RviVln3S/adP3/+zK3jIyGwBCo0m838LuJlCdjj8ViSJCl0lFmWyf/8z//kB/bLy8uFV6rMqxmj0Ug8z1va8cVxLI7jzJ0Rx3Es7XY77+h0h9hqtcRxHDk7O8uXvbm5kaOjo4Xf8x6MRiPpdrvieV7lVTx9ZWgwGNR6lShN07wudJCw7GrounXbbDbF87zCVZWfP3+WXhV6D95C+/z586d4nle4kUjkuQ51mfXvEHn/7VMH2iIid3d3lcv5vi/9fl++fv1a6/f/+vUr//+q619337m4uMhPTvWyH87WBt2BN8y+WUOMmzGUKuZ16WV1Hp6Zc1OV76bzfcTKybFzruz3dl6d/u4wDJXv+4Vym/lH5mfeYv7WInY9Vf1W88YavW2Ves7VMnO/Fq1vldwpnWNp1oVSm6tbc/p7za+07ap9lu1Dq9ShvsHDnGd66+3T/m3my859LquzNE3zbVyVO1zWdqvodZh1aN7wZn6/WXb7/ar7jtlvfLT8SqWUaij1fw+VArAz+lEZ9pUNvH2j0Uiurq4+XJ7Ve0L7fNt0XrV95RGbwVA4AAAAakFgCexYEAQyHo9lMpksfNA23p7RaCT9fn+lPEDsJ9rn26avVoo8/7WfVe/8x8sxFA4AAIBacMUSAAAAtSCwBAAAQC0ILAEAAFALAksAAADUgsASAAAAtSCwBAAAQC3+s+sC6L8bCgAAgMX2/SmROw8s930DAQAAYDUMhQMAAKAWBJYAAACoBYElAAAAakFgCQAAgFoQWAIAAKAWBJYAAACoBYFlDeI4lkajUfnKsixftt1uly4zGo1ERCQIgtL5QRDUVk6zPNiNdrud17mIyGg0Kq13bTqdzu0r2D1dLyazP3Bdt/Kzo9FI2u32pouIEmZ7ajQaEsfxwuVd163sg3XbXYS2Ww99fFzUrsz2V1avVfWVZdla+wQWUKiN4zgqiqK5aSKiwjDMpyVJosxNH4ZhYZk0TZWIqDRNlVJKRVGkRET5vv/isvm+r0SksF7shl3fepopiqK8vu39wfO8uf0Mu6HblFbWth3HmfucXs7zvK2UE0Wr9qW67VX1v57nze0DJt3Waa+vo+thWXux25/jOCpJkvz9ovpyHCfvh/V6OFa+DIFljcoCS6X+7cx6B7d3fv1ZfQCyAwlzHa9BY9m9JEnyYMM8kbB5npfvL77vFw5qSZKUBivYLh3gm+3S9/25kwT74KY/6/s+geUOpGk6V0fL6PoqY+8Dy6ZjfasG557nFeo2iqK5NlZVL+Yxuuw9VsdQ+BZcXl6KiMjNzU3lMosu7YuINJvNWsuE3RgOh9Lr9QrT7LrNskxms5m0Wi0REbm7u5OTk5N8/qdPnyRNU1Iadmg0GslgMJibnmWZ/PnzpzDNdV359etX/r7dbsvt7e3Gy4hyP378kH6/v/G0oMFgIGEY1prO9BGNRiPxfV8Gg8FcipBtMpnIly9f8vefP3+WyWSy0vd4nicXFxci8jyc7vt+3gdjPQSWW6ADh6pOLI5jmUwmcnZ2Vjp/Op3KeDwWz/M2VkZs3qoBxe/fvwv7Qpqm8vnz5/y93p/+/v1bfyGx1HQ6FREpPeicnp7KeDwutPXZbJb/vyogxfZ8//5dlFISRZE4jrORgG86nUqapiLy/GeLkySR8XhM3t4LXF1dSZZlcnd3J0opcRynNDdZt7lPnz7l0/T/VzmB0H1zo9GQh4eH/IIQ1rfzvxX+kZlnXr7vz+3IjuPk//c8j6scb9g6AcX19TXBxx4bDoeVbbHX68n9/X2h7YqIfPnyZWFAiu3RJ2adTkeOjo7EcRz5+vVrrfXy69cv8TwvH51otVrieZ5cX19Lp9Op7XveuyzLJE1Tubu7y+ttOBxKt9uVLMtqH8lzXVfOzs5kPB7LyckJdfVCBJZboM+WTk9PC9OVUgs/l6bp0oYTx7F0u938fRiGc0Ot2L1+v1867f7+vhCk2MPgIs8nGE9PT4VlRIpn5tiO0Wgkk8lkbjiu0WhIkiTSarUK9TkajeTq6kparZa0222ZTCZz+0Kj0VjaF2Azms2m+L5faF+bcnp6Kvf39xv/nvfu6OiodLo5kmOP6qwSgLquK9fX19JqteTk5ES63a58/vyZE8EXYCh8C/RQy/n5ee3r7nQ6op5vwhKlFEHlnjLrSA/nhGE4d+Xr58+f8u3bt8K0s7MzeXx8zN///ftXHMch73YHer1eoR6jKBKR5/q1D0BZlkm/35fhcCgiz0Nt5md93xfP8wgq94CZalKHL1++lOb22RcXsFiz2RTHceT379+F6VX9n+d5hZOEp6enlZOpmzwAACAASURBVFLI9JVRfbLe6XTE87xCbjRWR2C5Ya7rymQykSiKCASw1NXV1dwJyPfv3wtXuS4uLvJgBfspjmNxHEeiKGI4bY9tKj2h1WoV8jf1ScYmLi68d9++fSuMygVBMHfyrQ0Gg0IaUbfbXSmtSB+bf/78mU+zbwTCGrZ7E/r7pB9fUPUymc/REutZhkoVnzcpr3x2pUk/T02/eK7abpmPG9KSJKl8/Ix+VFTZPoPdsR9dYrazZXjc0G6Y/aC9/XX92Y+d0S/7MV92f20/nkY/x7hsHlZntivzmFhWX+bx2D7OLaov85mlHCNfp6EU4zAAAAB4PYbCAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILCsQRzH0mg0Kl9ZluXLttvt0mVGo5GIiARBUDo/CIJXlXE0GuXrarfbr1oX8NFlWVbafm2u60ocx3PTF30Gm+e67tp9q+67zf5z1X41CIJX9+EfmXncXNRuqo7F+hi8qL6m02nhM3g5AssadDodUUqJ4zgSRZEopfKX4zjiOE7eGG5vbyVJEhGRfJkwDKXf78toNJLLy0tJ01RERNI0FaWURFEk4/H4xR2TPrDp75tMJnRywCv8/Pkzb59KKen1enPLBEGQt2VNH7ywO0EQiOu6ed2Nx+PS4F/TddZsNkUpJbe3tyLy3K9eXV3l62k2m6XBZRzHMh6PN/Z73rsgCPJtr5SSq6uryuDy8fGxcPxNkkQ8z5Nms7mwvrIsk+FwmM/zPE9c193mz3xfFGrjOI6Komhuuud5SkRUkiRKKaWSJFH2pnccRzmOo5RSKk1TJSIqTdO5dbyEXaYwDPPvArA+3/cXzo+iSEVRpESktE9wHEeFYbip4mEBz/MK295+b9J9se677fXYdWv322maKt/3led5S/cZlLO3aZIklccvczmlntuprqNF9WVP18doe31YDVcst+Dy8lJERG5ubiqXWXZ21Gw2X/z9nU6n8P7g4ICzsR2xUx1M5vTpdFqYZw4FLbq6gs0bjUYyHo9L60nk+erHw8PDXLvDfjg9PZV+vy9ZlkmWZTKbzUqvOIuI/PjxQ8IwlOPjY2k0GoV+czabyePjY2F5x3Hk9+/f+fsgCPL+H+vTQ9h///7Np3369EnSNC2kmGn2cXI8HuftcFF92W3106dPpevDaggst0DvnGUNQeR5qGQymcjZ2Vnp/Ol0KuPxWDzPq6U8Dw8PMhgMalkX1qeMoRrNHJrTBzK9vwRBIIPBIB/a6Xa7uyo6ROT8/Dyvi+Pj47nhT4KJ/dbr9cT3fXEcR87OzmQ2m1UuOx6P5f7+Pm+baZrmaURnZ2fS7/cLy5upD+wHr9dsNsVxHBkOh/k0M8hcZDqdFo6Zy+rL9Pv3bwnD8AUlhogwFF6nqqFwpZ4vuXuep5T6d5ndfJnDJHr4xXzpz76WHprB9oVhWDq0kiTJ3HQxhlDL5mF/mHXl+36hvoSh8L3k+74Kw3Cu7zWVpSzpz2iO48z11Xpo1ax3hsJfrux4uEoqlzkMrlXVl62u4+1HxRGqRlWBpW4Y+kBS1mGVLb9KfofO49KvZQcrGszurHOS4DjOynld2K0wDPOTBvugVXbiqBSB5S7poFKp+b7ZVNZPL+q7dS6lUuUBzKoBERZbte0sOwE368ueTm7l6zAUvgV66OT8/Lz2des70vWrKldI5DlPj6GZ3ciyrDD8XZWfp5d1XVdarVY+TT9GYzKZbKW8WM/BwUHhzlWzrqMoot3tkbu7Ozk4OBCR56HWMAzl/v5+bjnd/ux2WpaSpNOVdIrRbDYr7Aee54nv+wuH3bHcaDSSNE0XHudEnvtL3/cr59v1Za7/5OSE3MpXIrDcMNd1ZTKZSBRFO91Z2+22DAaDvAzT6ZSbQLbIrPvb21sJw1AuLi5Kl/3x48dcIKJPIMIwlG63S93tiSzL5P7+nht13hDXdeX6+jp/f39/L6enp6XL+r5faKcXFxdz7XY0Gsnx8bEkSVI4GUS92u229Pv9Qm56levra/n69WvpvKr60o8wMtsyj+V7oV1cJn1v7OFo+2XSjw2SiqFr3/cXDqG9xCrlwvaV1YGdm1Vm0eNRsHnmMOeyoU2xcizt4XJSU3bDrEOzj9U5lGYaitknm+1OT19leJscy5fTdVW2/crqK03T0jpZVF/2cVm/ytKRsFxDqRXCfwC1c123MDQ2nU7l5uZm6bBpEARyeHi4dDgIAIBtI7AEdiAIAvn69Wshj2s4HOZ/1UMvYweZWZaJ4zgrDQcBALBt5FgCW2D/DduTk5M8qNQ5P5PJpLDM4eGhiBQfnH52dkZQCQDYW1yxBAAAQC24YgkAAIBaEFgCAACgFgSWAAAAqAWBJQAAAGpBYAkAAIBaEFgCAACgFgSWAAAAqAWBJQAAAGpBYAkAAIBaEFgCAACgFgSWAAAAqAWBJQAAAGpBYAkAAIBaEFgCAACgFgSWAAAAqAWBJQAAAGpBYAkAAIBaEFjWII5jaTQala8sy/Jl2+126TKj0UhERIIgKJ0fBMGryjgajWpbF4Bn0+lUGo1GYZrZH7iuO/cZs11Pp9NtFRUG13XX6g9d1y1dzuxX7f3AFAQB/e6a9LYtYx5Hl1m0rNlW4zguzDOPxfr4jBUp1MZxHBVF0dw0EVFhGObTkiRR5qYPw7CwTJqmSkRUmqZKKaWiKFIionzff1G5oigqfL+IqCRJXrQuAP+ISKEtl7Vtx3Hy92Yfods5bXG7fN9Xnufl70Vkrt/WdB2V9b+6rnU/ba9Xe23//RF5njfXtjTf9/NtmSRJoX2ts6zdVh3HydtiGIZz7VTXM5bjiuWGzWYz8TxP+v1+5dWJXq8njuPI1dVV6fxOpyOe58l4PH5RGY6OjqTX6+XvPc970XoA/NNutyWKosK0m5sbCcMwf6/b3XQ6zdt/p9MREZFmsylhGMrNzc2WSgwRkSzL5PT0NH/veZ48Pj6WLttsNkUpVdpnPj09ieM40mw2RUTk5OREZrPZ3Hc9PDzQ567p9vZ2rm2JPG/P8Xgs379/FxGRVqslruvOXW1cZdnhcFhoq8PhUIbDoYiInJ+fF9qp4zj1/sB3jsByCy4vL0VEFh5AyobMTLrzegnzs6PRSJrNprRarRevD6/XbrfnhlcWDc+ZwzIMqe3eaDSSwWAwNz3LMvnz509hmuu68uvXL3l6epI0TQvzDg4O5O7ubqNlRdHp6an0+33JskyyLJPZbFY48V7V0dGRpGmat+Pr62u5vr4uLBMEQd7/4/V+//5dCOZFno9vDw8Pay87mUzky5cv+bzPnz/LZDLJl9OCIJBv37696hj80RBYboHeIc1cS1McxzKZTOTs7Kx0/nQ6lfF4/Kqz3izLpNFoSL/ff/E6UI/RaJR3YFoQBOK6riilRCkl4/E4P7MejUaSZVk+L8sygssd0lcey07OTk9PZTweF9q6vop1dHQkIlI4oai6UobN6fV64vu+OI4jZ2dnc1cZV9VsNiVJEun3+9JoNGQwGBT2CYLK+j0+Ps5dhDk8PCw9ti5aVi//6dOnfJ7+v56n86dfOlL4kRFY7pC+AtXtdsX3/blOyHEcaTQacnx8LJ7nye3t7Yu/Sw/pJEki4/GYwGRHdFBiD60sGp67uroqXB27vLyks9uh4XBYeYWr1+uJ53l52200GpKmqXz58kWazaZEUZQHIvpEr+qEEpsVhqGkafrqvlAPpx4fH+fT4jiWk5MTrnK9Ya1WS5RSeZvlBp7VEVhugT4DMgMHEcmvQCmlSs9s0zTN51cFlfYd6ct2/larJWEYVl49xWZVBSWLhufSNJWnp6d8WX2w4o7i7dNXm82TQhEp3OF9e3ubt9swDMVxnPxKVqfTyefpYfGvX7/u5sd8UEEQyOHhofR6PUnTVMbj8YuChul0KhcXF9Lr9fI8TH2FbDAYSLfbzfeTyWQi4/F4acoTFjs4OJi7wvznz5/SAH7Rsnr5v3//5vP0/+11dTod8X1/LsUF1Qgst0CfEZ+fn9e+bvNApZRaKVfo4OCg9nJguXa7XXmCsGh4zvO8whVLTgp2RwcR+qVvMFBKzQ2NZ1km/X4/vyHAFgSBeJ5HvvOW3d3d5X2gvoHq/v5+7fX8+vWrECheXl5Kmqb5iaG5n3ieJ77vv3jYHc90XqspyzI5OTlZe1nP8won7E9PT5XpZoeHh68t+odCYLlhruvKZDKRKIr2ZlhkMBiU3niAzam62cNWNjx3e3sraZrmVz/0MDoByf6K41gcx5EoivK7S036mXqvSW/By7iuW7jJ5v7+fm40aRUHBwcymUzyE72ym0VQr2azKb7v51eY4ziW2WxW2saWLWsfB7vdbmUf3e/387vLsYItPdboXdPPKat6mcznc4n1fEulnp+7Zc6v49ln9nfyPK7tq9o39HPvfN+fe46pvW9onufxTLw9odu+pp9JW9a1ms9ErHpuIrZDP1/Y7mN1/ZnPFjXbq/3MRLO+Fx1OabPrsY+D9rNeq55zqaevsqxSxWO32SbN/YMwaX0NpZSqO1gFsJjruvLt27c8dcF1XRkOh/nZ9Gg0kvv7+7krWnEcS7fblTRNuTICANg7DIUDe2CV4bkgCAgqAQB7jcAS2AO3t7cym83yPMpms5lfzdR/61Y/y5KgEgCwrxgKBwAAQC24YgkAAIBaEFgCAACgFgSWAAAAqAWBJQAAAGpBYAkAAIBaEFgCAACgFgSWAAAAqAWBJQAAAGpBYAkAAIBaEFgCAACgFgSWAAAAqAWBJQAAAGpBYAkAAIBaEFgCAACgFgSWAAAAqAWBJQAAAGpBYAkAAIBaEFjWII5jaTQala8sy/Jl2+126TKj0UhERIIgKJ0fBEFt5XVdV+I4rm19wEeTZVlp+zVNp9N8/nQ6zaebnzOnY7NGo5E0Go256WY9ua67cB1l/Xe73Z77jqq6dV239HOYV1Vf5ryyY6zNrDObWR9mfdntW784bq5IoTaO46goiuamiYgKwzCfliSJMjd9GIaFZdI0VSKi0jRVSikVRZESEeX7/qvL6Pu+EpG5cgJYXRiGefss43leoQ1rZh+h23mSJBstK/7Vh33IS9NUeZ5XWM7sq01JkszVle/7eX1GUaQcx8nn2fWfJAn97oqq6ktb9Vjo+36+bJIkhfrxPK9wjDXnle0DhEurY0vVqCywVOpfI9Gdkh1Y6s/qHdsOLM11vEYURXmQSgcHvNyiA5vv+4VgRbMPbEo9H8DqOGHEcrrvM9mBfxiGlYFl2YmEuT67/7frlnpeT1l96emrnIxVHUfNEztzWbNt2nUdRRH1twaGwrfg8vJSRERubm4ql1k2BNNsNl9VhizL5OHhQTqdzqvWg9exUx1M5pBc1bCLHqJZNPSDzRqNRjIej0uHO7Msk/F4LKenp3P1+PT0JGmaFpY/ODiQu7u7rZUdRWa/Op1O5erqSnq93tJlRZ5ToHzfF5Hnek/TVI6OjvL5Zt1Op9N8nylLm8DqBoOBHB8fLz1m/v79WxzHKdRbs9mUh4eH/P/a2dmZXF9fF5YzXV9fy9evX+so/odAYLkFeietCgbiOJbJZCJnZ2el83Wn5Hnei8sQBEEe4GK31PNIgSilCtNvbm4K88pOAqr2EWzP+fm5KKUkSRI5Pj4u5Mr9/Pkzb6dKKQnDULrdrmRZlgcdZmDx+Pi43cKjlOu6cnx8vNZnHh4e5OTkRERE/v79KyLFgOTz58/5icSnT5/ydt3v9ytzB7Hc3d2dKKXk7OxsYd7j4+PjXPB5eHhYOA7rXE37hM82mUyk1Wq9vvAfBIHlDukrGt1uV3zfnwv8HMeRRqMhx8fH4nme3N7evuh7CCr3w2g0ku/fv5fOy7JMDg8PF34+CAIZDoebKBrWoIOHVqslSimZTCb5we3+/l5OT0/zq176358/f0qz2ZQoivLAotFoSL/f52RhD8xmM1FKSZqmS6+EaePxeOURIDPgVEqJ53m13pD5kehteXl5KVEUSbfbffG6er2eKKXE9305Pj4uveHKvDKN1RBYboE+Qzo9PS1MN69OlQV+aZrm86uCSvuOdHuYRQ/N6SBVnyl3u106ti3r9/viOE7p3aA/fvzIA46yK9txHMvJyYl8/vx5G0XFGsIwXHjl0Rxp6HQ6eZvWV0kYYtsfSZIsvXolMh9sfPr0SUSKo1JPT0/iOE7p5weDAeksNeh0OuI4Tum2PDg4kNlsVpj258+f0rSyy8tLcRxHnp6e5uYxDL4+Asst0AHc+fl57es2D1RKqbn8oGazWZivh1+jKOIq5hZlWVbY/nZ+3vfv30UpJVEUieM4haCf/Nj9d3BwICLPJ4/39/dz8798+TI3LQgC8TyPIbY9ogPEZexgo9lsiuM4+ZC4yPNQ7KKr0a/Nm8c/Zdvy6Oho7iQhy7I8fcFWdqU6yzKZzWa00XVt/v6gj2PR44bM6WV3hZvK7mark10ebF8YhnN3CGv2Y2jMO4z1vrOpfQPrsR9Xo+uu6hE0moiU3jmOzam6y9jk+37lXeGafQexuX5dp8v68Kq2j39Wqa8wDBcey8z6rGqLSpU/sUGvf9n+gHkEljXQDaDqZTKfzyXW8y2V+vecSf3axCMOCCz3w6JOUz8fb9G+RR3uhj5ZFJHSg5EOKuz2b06n7rbL7lf1SZt+hnBVvZiPgdMWBRvm+sxH4tjfz4nhYlX1pU+sq46fZY/lK3smpt1Gq07yHMehrl6goZR1ayqArXBddy4HSAuCQL5+/To3BDOdTuX4+FjSNGUoDQCwd8ixBHYgCILCc9NMOveSvB4AwFtDYAlsgX33/snJSSFwNOcNh0NurAIAvEkMhQMAAKAWXLEEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsaxDHsTQajcpXlmX5su12u3SZ0WgkIiJBEJTOD4Lg1eU0v9t13VevD/iosiwrbb/aorZm9xfT6XSbRf+wRqORNBqNhctU1adJ130cx5XL6Ppvt9tzn6urP3/vqurLbnuL6sFcvmw513Ur16O/X7+wBoXaOI6joiiamyYiKgzDfFqSJMrc9GEYFpZJ01SJiErTVCmlVBRFSkSU7/svLluapoUyAHi5MAzz9mlb1tZe047xMp7nKRFRVYc83Qfb/bdN98VVy+q+vayORUQlSaKUet4H6I+rLaovx3Hybae3d1VbXFRfnufNHWN1/djr9X1feZ5X2+977wgsa1QWWCr1r5HYO639WcdxlFLzgaW5jpfiYAbUZ1F7WjQvSZKlwQs2QwcPq05fpCxQ0f227udNYRgWAhO9LKpV1Yu9jau2uf0Zs77SNJ37jBmwRlGUH4/L3mMxhsK34PLyUkREbm5uKpdZNjTdbDZf/P1Zlsl4PGYIZg/YqQ6mqvQJ+3PU4W6NRqO8PdnD2Mva2nA4lG63y9DaHhkMBhKG4avb148fPyQMQzk+Pp5Lgbi/v5fT09P8ve7PSYNYn+d5cnFxISLPaSW+70ur1VprHc1mc+4zruvKwcGBiIgcHR1JmqZ5SsT19bVcX1/XUPqPgcByC3QnYgcLWhzHMplM5OzsrHT+dDqV8Xgsnue9uAzq+eq03N3dlQYu2B5dF0qpfJrruvm0MAwLB7fRaCRZluXzsywjuNyh8/NzUUpJkiRyfHxcyKMTWdzWLi8v8zpelsuHzZtOp5KmqYhIXqfj8Xhp3l6Z8Xgs9/f3ef2naZq309lslgctmuM48vT09Pof8cHc3t6KyPOJ+MPDQ37h5rVms5l0Oh0ReT5mJ0ki/X5fGo2GDAaDtYPXD237F0nfr6qhcKWeL8XroRA9FG6+zOEzPUxivurM7yBfZDeW5eVpSZIU6sdxnMKwDcNo+0UW5OYtamvL8sNQr7KhVXuIWqnntKNl/aNd52XpTTpvU6nq/HvSIqotSlHwPE/5vr9SXqxSi9uoUs91ZQ+NJ0mS1yH97Xq4YrkF+oqFORQiUrxyVXbWlaZpPl+fpdnsO0xXuQLy/ft3mc1mL/gleI1+vy+O48xd4RIppjocHx8X9oc0TQtXNhhG2y9hGMrj42PpvEVtrdVqied58vfv300WD2uy++mX+vLlS/5/13Xn9pE0TeXz58+1fNdH4rquDAYDuby8lCiKpNvtvqov1J81r0hOp1O5uLiQXq8nSinxPI8nqayBwHIL9HDI+fl57evudDqFALXX6630ORrJdplD2SJSmp+n8yhtnufJYDAorAv7xR7mNC1ra58+faq7OFjRly9fZDKZzE1fN7jUQYndpnX60unpqfz58yefrtsww6vrybJM0jTN20yn0xHP8+TXr18vXt9wOJw7bv769avQbi8vLyVNU/reVe3oSum7tOhxQ8uGTUxld4XXyXzMAnYjDMPKuwz1EwDMOhIrNYKmux/SNF04bLqorUVRxCNntqhqaNVxnDwVadW+1+7TlXpOezDbtH08MNfreR51v8Siu8LNbScvuCtcqee6tvtgvR/o7zYfR8Rd4avj6FQD81lZywIA8/lcdgNRSuV5I/pVx2OCzDyRVRohtmNRcLionnR+EXZDnyyKyNzBZlFbs3OnqcPtsfvVskfNlM0zHwOn1Hx+vF2H5vfYfbtZ/9T9Yovqy25HZsBoP5avqr6qjtlmvdhtGatrKGXcmgpga1zXrcy/c11Xrq+v54bK4jiWbrcraZq+6hFUAABsAjmWwA4EQVD5XLQ4jsV13bmgMggCgkoAwF4jsAS2wL57/+TkpJDwb857eHgoPAVA/91hfQMQQSUAYF8xFA4AAIBacMUSAAAAtSCwBAAAQC0ILAEAAFALAksAAADUgsASAAAAtSCwBAAAQC0ILAEAAFALAksAAADUgsASAAAAtSCwBAAAQC0ILAEAAFALAksAAADUgsASAAAAtSCwBAAAQC0ILAEAAFALAksAAADUgsASAAAAtSCwrEEcx9JoNCpfWZbly7bb7dJlRqORiIgEQVA6PwiCWso6nU7zdU6n01rWCXw0WZaVtl8RkdFotLDd2v0F7XA7dL0sUlaf6yxr1r1dr2bfvsr6P7qq+rLbnnl8LWMec6vounFdd+77G42GtNvtl/+Qj0ihNo7jqCiK5qaJiArDMJ+WJIkyN30YhoVl0jRVIqLSNFVKKRVFkRIR5fv+q8rneV5hvQBeJgzD0nYURVGhrYuISpKksMxr2zHWp/u+qkOe7oPt/nudZaMoUo7j5O/NvjYMw3x5u3/HvEX1ZbYpfSyt2pa+7+ftLUmSQv0o9a8uPM8rTLfr0vf9uWVQjcCyRmWBpVL/GondGOzP6h25rOPR63gpGgZQn6rg0D7AeZ5XCCyTJFkpeEH99An6qtPXWYdS8/1/GIb5fmLvF47jEFguUbatoyiaO475vl84mdOqjqNmHVWdTNjL6WWps9UwFL4Fl5eXIiJyc3NTuYx5Cb5Ms9l88fdnWSbj8VhOT0/zS/txHL94fXg5O9XB5rru3PCpmb7AEOrujUYjGY/HpXVgttPRaCTNZlNarVY+bTgcSrfbXToki+0ZDAYShuFKaUdVy2ZZJmmaytHRUb7swcGB3N3diUhxvwiCQL59+/aqPv2jenx8lNlsVph2eHgo9/f3c8v+/v1bHMcpbOdmsykPDw8i8tw+fd+XwWAw1x/PZjN5fHwsrM9xHPn9+3edP+fdIrDcAr1jV+WCxHEsk8lEzs7OSudPp1MZj8fied6Lvv/nz5/5Z5VSEoahdLvdpbkp2Az1PFIgSql8ms4bStN0bvlfv34VPpOmqTiOUwhYsD3n5+eilJIkSeT4+Hgu/0rXZb/fn/vs5eVl3gbJtdu96XSatzldp+PxuPTEe9Gyf//+FZFiAPn58+dCe9YniOPxeJM/6V378uWLpGlaqJ8/f/6ULvv4+Dh3webw8DA/7l1dXUmWZXJ3dydKKXEcJ2/LZ2dnc+23rG9Ghd1cKH2fqobClVKFPA49FG6+zKE1fQnffL1mGNvzvLmhArHyPrF5VXl5Js/z5oZZ7c+EYUjd7RGpGE7T7bxq2HxZfhjqVTa0GobhXN/qeV5pf7to2bL0prJpZjlow4tVpR3oHFfzVbYty+pLTysbJtffp6fp+yPMF211NVyx3AJ9hnR6elqYroyrUHq43JSmaT7/9va2dN32HaarXgF56dVPvFy/3y+cFa/KHjK7urqS8/PzOouGVwjDcG7YTESk1WpJGIaVIwOtVks8z8uvdmE/2P30Kst++vRJRIqjUk9PT+I4ztxnOp2O+L5feaUNi/V6vfy4mCSJiEhpf3hwcDA3bP7nz5/KFAQzjUHkeThcf4/v++J5HukLKyKw3AKdh7OJYKDT6RQC1F6vN7fM6elpaQ7Kly9fai8PymVZVhj+fmmOpD5w0cHtl4ODg7Wmm3RQgu378uWLTCaTuellweWiZZvNpjiOUzhJeHx8rExvOjw8fEWpoV1cXIjv+6X94dHR0dzwdZZlcnJykteXnTNp52SK/EtFGwwG9f+A92oXl0nfq0WPGzKnVw2RaHU/jkKvT5fBfpQCti8Mw9I6KBsKtz/HENr+SNN0YZqK4zhzjxvS7EcTYbOqhlYdxyncvb2o7120rHnH8rL11Nm/v1eL7sDX23fZo7vMO8bt454eUtfKUsb0MlVtGOUILGugG0DVy2Q+n0tKckN836/MvXwNO28Tu1dWD8sCSx5Tsntm7pV9cmC3b7Ou7DbI8yy3x+5X7UDBrFNznvkYiI402QAAAY5JREFUuGXLKlXM/7PXQ/+7uqr6Mu9PKAv2yh7Lt+iZmGZ9me1Rfz8XYF6moZRxayqArXFddy4HqN1uS7PZLM25nU6nMhwOK/NtAQDYNXIsgR0IgkCur6/X+szNzY1cXFxsqEQAALweVyyBLYjjWLrdbv4+iiLpdDqFZcwH9DqOM3c1s9FoCM0VALDPCCwBAABQC4bCAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUAsCSwAAANSCwBIAAAC1ILAEAABALQgsAQAAUIv/7LoA5p+xAwAAQLV9/4OJOw8s930DAQAAYDUMhQMAAKAWBJYAAACoBYElAAAAakFgCQAAgFoQWAIAAKAWBJYAAACoBYElAAAAakFgCQAAgFoQWAIAAKAWBJYAAACoBYElAAAAakFgCQAAgFoQWAIAAKAWBJYAAACoBYElAAAAakFgCQAAgFoQWAIAAKAWBJYAAACoBYElAAAAakFgCQAAgFoQWAIAAKAWBJYAAACoBYElAAAAakFgCQAAgFr8fzAbJq6b4BiGAAAAAElFTkSuQmCC\"\u003e\u003c/p\u003e\n\u003cp\u003e\u003c/p\u003e\u0026nbsp;\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\u003eOscillator strength (f), Light harvesting efficiency of the DPP group of sensitizers.\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" rowspan=\"2\"\u003e\n \u003cp\u003eDye\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" rowspan=\"2\"\u003e\n \u003cp\u003ef\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" rowspan=\"2\"\u003e\n \u003cp\u003eLHE\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" colspan=\"2\"\u003e\n \u003cp\u003eTRANSITION ASSIGNMENT\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eMajor\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\"\u003e\n \u003cp\u003eMinor\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDPP \u0026minus;\u0026thinsp;1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.6862\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.7940\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L (86%)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-2-\u0026gt;L (10%)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDPP \u0026minus;\u0026thinsp;2\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.1993\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.9368\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L (73%)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-2-\u0026gt;L (14%), H-\u0026gt;L\u0026thinsp;+\u0026thinsp;1 (7%)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDPP \u0026minus;\u0026thinsp;3\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.1288\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.9257\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L (65%), H-2-\u0026gt;L (15%)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L\u0026thinsp;+\u0026thinsp;1 (12%), H-3-\u0026gt;L (4%)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDPP \u0026minus;\u0026thinsp;4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e1.8911\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.9872\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L (57%), H-2-\u0026gt;L (19%)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L\u0026thinsp;+\u0026thinsp;1 (13%), H-3-\u0026gt;L (4%)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDPP \u0026minus;\u0026thinsp;5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.2295\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.9941\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L (46%), H-2-\u0026gt;L (20%)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L\u0026thinsp;+\u0026thinsp;1 (19%), H-3-\u0026gt;L (8%)\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eDPP \u0026minus;\u0026thinsp;6\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e2.2875\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\"\u003e\n \u003cp\u003e0.9948\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-\u0026gt;L (37%), H-3-\u0026gt;L (25%)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"left\"\u003e\n \u003cp\u003eH-2-\u0026gt;L (24%), H-\u0026gt;L\u0026thinsp;+\u0026thinsp;1 (9%)\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\u003ch3\u003eElectrochemical Properties\u003c/h3\u003e\n\u003cp\u003eElectron injection (ϕ\u003csub\u003einj\u003c/sub\u003e) is the process of injection of electrons into the CB of the TiO\u003csub\u003e2\u003c/sub\u003e from LUMO during the photoexcitation process. The electron injection is determined by the thermodynamic driving force (ΔG\u003csub\u003einject\u003c/sub\u003e). ΔG\u003csub\u003einject\u003c/sub\u003e is calculated from the oxidation potential, vertical excitation energy of the sensitizers and reduction potential of the semiconductor.\u003c/p\u003e \u003cp\u003eΔG\u003csub\u003einject\u003c/sub\u003e of the sensitizers is determined from the equation [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e],\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$${{\\Delta }G}_{inject }=OPES - {E}_{CB}^{SC}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;..\u003c/p\u003e \u003cp\u003eWhere,\u003c/p\u003e \u003cp\u003eOPES is the oxidation potential of the sensitizer in excited state\u003c/p\u003e \u003cp\u003e \u003cspan class=\"InlineEquation\"\u003e \u003cspan class=\"mathinline\"\u003e\\({E}_{CB}^{SC}\\)\u003c/span\u003e \u003c/span\u003e is reduction potential of the semiconductor conduction band.\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$$OPES= RPGS- {\\lambda }_{max}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;..\u003c/p\u003e \u003cp\u003eWhere,\u003c/p\u003e \u003cp\u003eRPGS is the reduction potential in ground state\u003c/p\u003e \u003cp\u003eλ\u003csub\u003emax\u003c/sub\u003e is the vertical excitation energy of the sensitizers.\u003c/p\u003e \u003cp\u003eElectron regeneration is determined by the following equation [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e],\u003cdiv class=\"BlockQuote\"\u003e\u003cp\u003eΔG\u003csub\u003ereg\u003c/sub\u003e = RPGS \u0026ndash; E\u003csub\u003eredox\u003c/sub\u003e \u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;\u0026hellip;.. (3)\u003c/p\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere,\u003c/p\u003e \u003cp\u003eE\u003csub\u003eredox\u003c/sub\u003e is the oxidation potential of the redox electrolyte.\u003c/p\u003e \u003cp\u003eThe electron injection and electron regeneration of the sensitizers are listed in Table\u0026nbsp;\u003cspan refid=\"Tab6\" class=\"InternalRef\"\u003e6\u003c/span\u003e. All the designed sensitizers have a negative value of ΔG\u003csub\u003einject\u003c/sub\u003e and a positive value of ΔG\u003csub\u003ereg\u003c/sub\u003e, which means they possess the position of LUMO is above the conduction band of the semiconductors and the position of the HOMO is below the redox electrolyte. The lower negative value of ΔG\u003csub\u003einject\u003c/sub\u003e and the lower positive ΔG\u003csub\u003ereg\u003c/sub\u003e indicate that the DSSC is more efficient. The electron injection of the designed sensitizers is in the range of -0.970 to -1.344. Configuration 4 has the lower negative value of ΔG\u003csub\u003einject\u003c/sub\u003e and it has the greater number of π-spacers units. Configuration 3, on the other hand, has a lower positive value of ΔG\u003csub\u003ereg\u003c/sub\u003e. The above results reveal that the DPP-4 has the lower negative value of ΔG\u003csub\u003einject\u003c/sub\u003e and the DPP-3 has the lower positive value of ΔG\u003csub\u003ereg\u003c/sub\u003e value compared to other sensitizers.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab6\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 6\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eElectron injection (ΔG\u003csub\u003einject\u003c/sub\u003e), electron regeneration (ΔG\u003csub\u003ereg\u003c/sub\u003e) of the DPP group of sensitizers.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDyes\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eE\u003csub\u003eOx\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eλ\u003csub\u003emax\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eOPES\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eΔG\u003csub\u003einject\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eΔG\u003csub\u003ereg\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e5.2956\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.6400\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.656\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-1.344\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.496\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e5.2592\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.3691\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.890\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-1.110\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.459\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e5.2472\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.5355\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.712\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-1.288\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.447\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e5.2679\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.2375\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e3.030\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-0.970\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.468\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e5.3027\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.3014\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e3.001\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-0.999\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.503\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e5.2853\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.4000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.885\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e-1.115\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0.485\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e\n\u003ch3\u003eNlo Properties\u003c/h3\u003e\n\u003cp\u003eThe NLO properties are determined by the electronic properties of the sensitizers. The higher values of dipole moment and polarizability generate the electron hole pair in the DSSC [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. From Table\u0026nbsp;\u003cspan refid=\"Tab7\" class=\"InternalRef\"\u003e7\u003c/span\u003e, the dipole moment value of DPP-1 is found to be 7.9521debye. Configuration 6 has the higher value of \u0026micro; 18.5055 debye compared to the other configurations. One of the key criteria for greater polarizability is electron density. The polarizability values of the DPP sensitizers are increased in the order: DPP-1\u0026thinsp;\u0026lt;\u0026thinsp;DPP-2\u0026thinsp;\u0026lt;\u0026thinsp;DPP-3\u0026thinsp;\u0026lt;\u0026thinsp;DPP-4\u0026thinsp;\u0026lt;\u0026thinsp;DPP-5\u0026thinsp;\u0026lt;\u0026thinsp;DPP-6. With configuration 1, which has the lower value of α and the inclusion of π-spacers in configuration 2, the value was increased due to the increased electron density of the sensitizers. Similarly, because of the increased number and changed positions of π-spacers, configurations 4,5 and 6 have higher values. The configuration 6 of the DPP sensitizers has a higher value of α compared to the other configurations. According to the aforementioned findings, configuration 6 has a greater dipole moment and polarizability value, which makes it a better fit for DSSC applications.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab7\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 7\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eNLO properties of the DPP group of sensitizers.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eDye\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\" morerows=\"1\" rowspan=\"2\"\u003e \u003cp\u003eDipole moment\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003ePolarizability\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e(au)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003ex10\u003csup\u003e\u0026minus;\u0026thinsp;23\u003c/sup\u003eesu\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e7.9521\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e303.168\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.493\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e4.6716\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e346.692\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5.138\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e11.7348\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e364.861\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e5.407\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e8.9936\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e417.273\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e6.184\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e16.5646\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e464.125\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e6.878\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDPP \u0026minus;\u0026thinsp;6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e18.5055\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e484.457\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e7.179\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eDFT and TD-DFT functions in the B3LYP/6-311G(d,p) basis set are used to investigate six diphenylamine functionalized perylene-based sensitizer configurations. The NBO analysis reveals that configuration 2 has the higher positive value of q\u003csup\u003eD\u0026minus;A\u003c/sup\u003e and possesses better electron donating ability when compared with the other configurations. Frontier molecular orbital analysis and NLO properties results reveal that the numbering and changed positions of the π-spacers are influenced by the HOMO-LUMO energy gap, dipole moment, and polarizability values. The absorption spectrum analysis reveals that configuration 6 has the red shift of the absorption spectrum, a higher molar extension coefficient, and higher LHE values, so configuration 6 is the better candidate for DSSC applications. The electron injection and electron regeneration results reveal that configuration 4 and configuration 3 have the best ΔG\u003csub\u003einject\u003c/sub\u003e and ΔG\u003csub\u003ereg\u003c/sub\u003e values compared to the other configurations. All the above discussion reveals that configuration 6 has the lower HOMO-LUMO energy gap, higher \u0026micro; and α values, red shift of the absorption spectra, higher ε value and higher LHE values and it reveals that DPP-6 is the better candidate for DSSC applications.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor Contributions:\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e1) D.Nicksonsebastin \u0026nbsp; \u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cul\u003e\n \u003cli\u003econception or design of the work,\u0026nbsp;\u003c/li\u003e\n \u003cli\u003e\u0026nbsp;acquisition, analysis, or interpretation of data,\u0026nbsp;\u003c/li\u003e\n \u003cli\u003edrafted the work or revised it critically for important intellectual content,\u003c/li\u003e\n \u003cli\u003eapproved the version to be published\u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003e\u003cstrong\u003e2) P.Pounraj\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cul\u003e\n \u003cli\u003econception or design of the work,\u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003e\u003cstrong\u003e3) E. Isac Paulraj\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cul\u003e\n \u003cli\u003eacquisition, analysis, or interpretation of data\u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003e\u003cstrong\u003e4) N.Mani\u0026nbsp;\u003c/strong\u003e\u003c/p\u003e\n\u003cul\u003e\n \u003cli\u003edrafted the work or revised it critically for important intellectual content\u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003e\u003cstrong\u003e5) M.Prasath\u003c/strong\u003e\u003c/p\u003e\n\u003cul\u003e\n \u003cli\u003econception or design of the work\u003c/li\u003e\n \u003cli\u003eacquisition, analysis, or interpretation of data\u003c/li\u003e\n \u003cli\u003edrafted the work or revised it critically for important intellectual content\u003c/li\u003e\n \u003cli\u003eapproved the version to be published\u003c/li\u003e\n\u003c/ul\u003e\n\u003cp\u003eThe first draft of the manuscript was written by\u0026nbsp;\u003cstrong\u003eD.Nicksonsebastin\u0026nbsp;\u003c/strong\u003eand all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript\u003c/p\u003e\n\u003cp\u003eThe authors declare that no funds, grants, or other support were received during the preparation of this manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting Interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors have no relevant financial or non-financial interests to disclose.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of data and material:\u003c/strong\u003e Not Applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCode availability:\u003c/strong\u003e\u0026nbsp; Not Applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics approval:\u0026nbsp;\u003c/strong\u003eNot Applicable\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003ePanan H, Beibei A, Hehe R, Yuhang H, Xugeng G, Lemin M, Li W, Jinglai Z (2020) Influence of Different Molecular Design Strategies on Photovoltaic Properties of a Series of Triphenylamine-Based Organic Dyes for Dye-Sensitized Solar Cells: Insights from Theoretical Investigations J. 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J Comput Electron \u003cstrong\u003e13\u003c/strong\u003e, 1033\u0026ndash;1041. https://doi.org/10.1007/s10825-014-0628-2\u003c/li\u003e\n\u003cli\u003eMahmood A, Hussaintahir M, Irfan A, Khalid B, Al-Sehemi A G (2015)\u003cstrong\u003e \u003c/strong\u003eComputational Designing of Triphenylamine Dyes with Broad and Red-shifted Absorption Spectra for Dye-sensitized Solar Cells using Multi-Thiophene Rings in \u0026pi;-Spacer. Bull. Korean Chem. Soc. 36, 2615-2620. https://doi.org/10.1002/bkcs.10526\u003c/li\u003e\n\u003cli\u003eBai Y, Zhang J, et al. (2011) Engineering Organic Sensitizers for Iodine-Free Dye-Sensitized Solar Cells: Red-Shifted Current Response Concomitant with Attenuated Charge Recombination. J Am Chem Soc 133:11442\u0026ndash;11445. https://doi.org/10.1021/ja203708k\u003c/li\u003e\n\u003cli\u003ePrakasam M, Anbarasan PM (2016) Second order hyperpolarizabilityof triphenylamine based organic sensitizers: a first principle theoretical study. RSC Adv 6:75242\u0026ndash;75250. https:// doi. org/ 10.1039/ C6RA1 1200E\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"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":"Diphenylamine, perylene, LHE, DFT","lastPublishedDoi":"10.21203/rs.3.rs-2603551/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-2603551/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe novel sensitizers are framed by perylene as donor with diphehylamine as auxiliary donor, thiophene and cyanovinyl as π-spacers and cyano acrylic acid as an acceptor unit. The optimised structure for the designed sensitizers was determined utilizing density functional theory, and the electronic structure was determined utilizing time-dependent density functional theory through the B3LYP/6-311G (d, p) basis set in the gas phase and Dimethylformamide (DMF) phase. The frontier molecular orbital results have significantly lower HOMO-LUMO energy gap values for better electron injection and electron regeneration. All designed sensitizers have absorption spectra values in the range of visible to near IR region. In the present work, the position and number of π-spacers reduces the HOMO-LUMO gap, the redshift of the absorption spectrum, and increases the high light harvesting efficiency. The findings reveal that the number of π-spacers improves the power conversion efficiency (PCE) of the solar cells.\u003c/p\u003e","manuscriptTitle":"Screening the effects of additional donors, numbers and positions of π-spacers on perylene- based sensitizers in dye-sensitized solar cell applications","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-03-06 23:29:58","doi":"10.21203/rs.3.rs-2603551/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","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}}],"origin":"","ownerIdentity":"39885753-85a0-432a-92c7-c046c5a44412","owner":[],"postedDate":"March 6th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-06-22T05:07:51+00:00","versionOfRecord":{"articleIdentity":"rs-2603551","link":"https://doi.org/10.1007/s11696-024-03429-y","journal":{"identity":"chemical-papers","isVorOnly":false,"title":"Chemical Papers"},"publishedOn":"2024-04-09 05:07:51","publishedOnDateReadable":"April 9th, 2024"},"versionCreatedAt":"2023-03-06 23:29:58","video":"","vorDoi":"10.1007/s11696-024-03429-y","vorDoiUrl":"https://doi.org/10.1007/s11696-024-03429-y","workflowStages":[]},"version":"v1","identity":"rs-2603551","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-2603551","identity":"rs-2603551","version":["v1"]},"buildId":"-HB7Z8yhvgn0wM9Nzuekk","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}