Tailoring Plasmon Hybrid States in Peropyrene Heterodimers by Charge Doping and Static Electric Field

Tailoring Plasmon Hybrid States in Peropyrene Heterodimers by Charge Doping and Static Electric Field | 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 Tailoring Plasmon Hybrid States in Peropyrene Heterodimers by Charge Doping and Static Electric Field Haoran Liu, Nan Gao, Yongqi Chen, Yurui Fang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9229438/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 23 Apr, 2026 Read the published version in Plasmonics → Version 1 posted 7 You are reading this latest preprint version Abstract Plasmon hybridization, as a basic interaction mechanism in nanophotonics research, has gained significant attention due to its clear picture in light-matter interaction properties. This hybridization can generate modulate spectral responses, and potentially enable the design of novel photonic devices. In this study, we employ peropyrene heterodimer as a model system and apply ab initio quantum mechanical calculation to systematically investigate the regulatory effects of charge doping and static electric fields on molecular plasmon hybridization behavior. Our results reveal that charge doping significantly alters plasmon hybridization modes, transforming strong hybridization states into a single molecule dominated plasmon excitations or even inducing new hybridization effects. Moreover, electric field regulation offers more precise control, allowing fine-tuning of hybridization strength while maintaining the original framework. These findings characterize the plasmon hybridization mechanisms at the molecular scale, which may be relevant for exploring tunable nanophotonic applications based on molecular plasmons. Molecular Plasmon Plasmon Hybridization TDDFT Regulate States Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 1. Introduction Plasmon hybridization, as a crucial analyzing method in nanophotonics, has attracted significant attention in recent years due to its unique role in light-matter interactions. 1 – 6 Traditional plasmonic studies on metallic nanoparticles have established a relatively complete theoretical framework, with the plasmon hybridization theory initially proposed by Nordlander et al. in 2003. 7 This theory successfully explains the coupling mechanism of surface plasmonic resonances (SPRs) in metallic nanostructures and provides an intuitive description of the interactions between different plasmonic excitations, laying an important foundation for the design of nanophotonic devices. 8 , 9 Although this theory has achieved notable success in studying macroscopic nanostructures, as the system decreases to molecular scales, quantum effects become increasingly prominent, 10–13 posing new challenges for a deeper understanding of the fundamental physical mechanisms of plasmons. As an ab initio quantum mechanical approach, time-dependent density functional theory (TDDFT) 14 – 16 provides a rigorous theoretical framework for characterizing plasmonic excitation properties at the molecular scale. 17 – 27 In recent years, TDDFT and its approximate methods have been increasingly employed to investigate the optical properties of metallic nanocluster dimers. 28 – 34 However, research on plasmon hybridization and its tunability in molecular scale systems remains relatively scarce, despite their established ability to support plasmonic excitations. 31 , 34 – 36 In contrast to conventional metallic nanostructures, conjugated molecular systems (e.g., polycyclic aromatic hydrocarbons, alkene chains) offer unique advantages. Their structural precision enables angstrom-scale control over plasmonic responses, and rich chemical modification strategies provide versatile pathways for dynamically tuning plasmonic strategies. These characteristics endow molecular plasmonic systems with promising potential for applications in nanophotonic device development. 36 – 38 As a prototypical class of molecular plasmonic systems, peropyrene and its derivatives have been studied, with their optical properties comprehensively characterized in prior works. 39 Building upon this foundation, the present work investigates the modulation mechanisms of plasmon hybridization in peropyrene heterodimers through charge doping and static electric field manipulation. Using linear response TDDFT (LR-TDDFT) calculations complemented by plasmonicity index (PI), 40 generalized plasmonicity index (GPI), 41 transition contribution map (TCM), 42–45 single-particle component analysis (SPCA) 46 – 49 and charge transfer characterization, we investigate the optical responses and hybridization characteristics of two distinct heterodimer configurations. When constituent monomers exhibit proximal plasmonic resonance energies, the heterodimer demonstrates remarkable hybridization phenomena, manifesting as characteristic bonding and antibonding excitation mode. Comparative analysis of modulation approaches shows that the charge doping exerts more pronounced effects on hybridization tuning than external static electric field. Notably, through deliberate design of heterodimer composition, charge doping can activate hybridization effects that are absent in neutral states. These findings characterize plasmon hybridization mechanisms at the molecular scale, hinting at possibilities for future dynamically tunable nanophotonic devices based on molecular plasmons. 2. Methods All LR-TDDFT calculations based on the Casida’s equation solved in the basis of Kohn-Sham particle-hole transitions are performed using the Gaussian 16 software. 50 The study focuses on two distinct heterodimer configurations, one consists of peropyrene-N (modified with nitrogen atoms) and peropyrene arranged along the x -axis (peropyrene-NC), and the other comprises of peropyrene-N and peropyrene-O (modified with nitrogen and oxygen atoms) aligned along with x -axis (peropyrene-NO). The initial monomer geometries are adopted from our previous work. 39 All heterodimer configurations, including those under charge doping and external static electric field, are fully optimized to their equilibrium structures. Consequently, inter-molecular spacing varies slightly across different conditions, this parameter is not investigated systematically in the current study. Consistent with our prior research and to ensure balanced accuracy between plasmonic excitation characterization and computational feasibility, we employ the TPSSH exchange-correlation functional 51 , 52 with the 6-311G(d,p) basis sets 53 and the DFT-D3(BJ) dispersion correction 54 , 55 for all calculations, including geometric optimization, ground-state electronic structure, and absorption spectra simulations. To achieve a reliable description of excited states, we include all orbital transition contributions with an oscillator strength threshold of 10 − 5 . Spectral broadening is modeled using Gaussian damping with a width parameter of 0.20 eV. For charge doping investigations, we characterize the optical properties of peropyrene-NC for charge states between − 2 and + 2, whereas peropyrene-NO is examined over a broader range (− 4 to + 4). In the case of static electric field effects, both heterodimers are analyzed under field strengths from − 0.004 a.u. to + 0.004 a.u. applied along the x direction. Computational settings for charged and field-modulated systems remain identical to those of the neutral state calculations. Plasmonic excitation characteristics are evaluated using PI, GPI, TCM, SPCA analyses, as detailed in earlier publications. 39 – 49 Atomic charge distributions are quantified using the atomic dipole moment corrected Hirshfeld (ADCH) population method, 56 chosen for its superior general applicability and physical soundness. 57 Concurrently, the interfragment charge transfer (IFCT) 58 based on the default Mulliken-like partition, is employed to quantify electron redistribution (both between and within individual monomers), with each molecular unit treated as a sepa rate fragment. All post-processing of ground-state electron structures, excited-state properties, ADCH and IFCT analyses are performed using the wave function analysis software Multiwfn 3.8(dev). 58 , 59 For visualization, molecular structures and date plots are rendered using VMD 60 and VESTA 61 software. 3. Results and Discussion 3.1 Single-Molecule Plasmonic Excitations Building upon our systematic investigations of plasmonic excitations in peropyrene and its derivatives (peropyrene-N and peropyrene-O), 39 we establish monomeric optical properties as the foundation for heterodimer studies. Figure 1 a-c present the absorption spectra, PI values, and optimized structures of these three systems. To further strengthen the reliability of our findings, we calculate the GPI values for the first ten excited states. The PI and GPI values exhibit highly consistent evolutionary trends (see Table S1 -3 in the Supplemental Material (SM)), reinforcing the robustness of our results. Though minor spectral blue-shifts are observed due to differences in exchange-correlation functionals (see Figure S1 in the SM), the overall spectral evolution remained consistent, validating our computational approach. Additionally, Figure S1 d in the SM demonstrates that subtle geometric variations in peropyrene-N across different heterodimer configurations do not significantly alter its absorption characteristics. Hence, we select peropyrene-N monomer form peropyrene-NC heterodimer structure for further single-molecule analysis. TCM provides an effective framework for characterizing plasmonic excitations. Thus, we compute TCM and transition densities (see Fig. 1 d-f) for the first excited state S 1 (S 0 →S 1 ), where the PI values peak. The TCM unambiguously reveals the plasmonic nature of the excitations, while the transition densities confirm a longitudinal dipole plasmonic resonance mode, aligning with prior theoretical findings. Due to the small molecular size, the Kohn-Sham states exhibit discrete energy levels, leading to relatively weak collective excitations, as evidenced by the TCM wherein the plasmonic excitations predominantly arise from the HOMO→LUMO transition. 3.2 Plasmon Hybridization Properties of Heterodimers Furthermore, we conduct an analysis on the excitation characteristics of peropyrene-NC heterodimer composed of peropyrene-N and peropyrene, as well as peropyrene-NO heterodimer formed by peropyrene-N and peropyrene-O. During this process, we only consider the peropyrene heterodimers placed along the x -axis, and the specific geometric structure diagrams can be referred to in Fig. 2 a-b. It should be noted that since we directly perform geometric optimization on the heterodimer configurations, the molecular spacing in the two heterodimers are not the same. Therefore, the influence of inter-molecular spacing is not analyzed in the current investigation. Through computational analysis, we obtain the total absorption spectra (dashed line) and corresponding PI values for the heterodimers, as presented in Fig. 2 c-d. In addition, we further provide the excitation energies, oscillator strengths, and GPI values corresponding to the first fifteen excited states, the relevant data are listed in Table S4-5 in the SM. The results demonstrate a strong correlation between PI and GPI values evolution trends, with both heterodimers exhibiting two distinct plasmonic excitation modes within specific spectral ranges. To further analyze these modes, we extract the absorption spectra corresponding to the plasmonic excitations, which are shown as solid lines in Fig. 2 c-d. In previous research work, it has been found that for the structures composed of molecular systems supporting plasmonic excitation modes, their plasmon responses can be effectively described using the plasmon hybridization model. Therefore, our subsequent analyses employ this framework to investigate the observed plasmonic behavior. The hybridization effect is predominantly governed by the intermolecular interaction strength and the resonant energy alignment of the initial plasmonic modes. As illustrated in Fig. 1 a-c, while peropyrene and peropyrene-N exhibit colsely matched plasmonic resonance energies, peropyrene-O demonstrates a pronounced energetic detuning. This energetic mismatch results in significantly plasmon interaction in peropyrene-NC compared to peropyrene-NO, leading to distinct hybridization phenomena exclusively observed in peropyrene-NC. We firstly analyze the excitation characteristics of peropyrene-NC. Figure 3a presents a schematic diagram of the plasmon hybridization modes in peropyrene-NC, comparing the transition densities of plasmonic excitation modes between monomeric and dimeric structures. The transition densities clearly identify low-energy bonding and high-energy antibonding plasmonic resonance modes formed by hybridization. Quantitative analysis shows that the bonding state exhibits a 0.031 eV energy shift relative to peropyrene’s isolated resonance, while the antibonding state shows a 0.019 eV energy shift relative to peropyrene-N’s resonance. These substantial energetic perturbations unambiguously confirm the presence of strong intermolecular interactions. Owing to the short interdimer spacing and electronic perturbation induced by nitrogen and oxygen atoms doping, charge transfer occurs in the dimers under equilibrium conditions. Thus, we calculate the charge distribution of peropyrene-NC, as shown in the lower-right inset of Fig. 3a, where blue represents negative charge and red represents positive charge. Quantitative analysis of total charge on peropyrene-N (indicated below the inset) confirms a net charge of 0.0604 a.u., demonstrating weak intermolecular charge transfer. Such minute charge quantities are inaccessible in monomeric structure calculations, potentially introducing unavoidable errors into the actual analysis. Figure 3. Plasmon hybridization mechanism and orbital analysis in substituted peropyrene-NC. (a) Schematic diagram of plasmon hybridization in peropyrene-NC, including the transition densities for both monomeric and dimeric plasmonic excitation modes. The red numerical values indicate the energy deviations of the monomeric resonance relative to the corresponding hybridization modes. The inset in the lower-right corner (green dashed box) displays the ground-state atomic charge distribution, with the green value indicating the net atomic charge accumulated on peropyrene-N. (b-c) TCMs for the (b) bonding state and (c) antibonding state of peropyrene-NC. The insets depict the transition dipole moment contribution maps for the respective hybridization states, with red arrows represent monomeric contributions, green arrows denote total contributions, and arrow orientations indicate the transition dipole directions. (d) SPCA of bonding and antibonding states for peropyrene-NC. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-1, HOMO, LUMO, LUMO + 1). Green arrows highlight the dominant orbital transitions involved in the excited states, and blue numbers indicate their relative contributions. Figures 3b-c show the TCM and density of states (DOS) for the bonding and antibonding states of peropyrene-NC, where the yellow region in the DOS plot signifies the contribution from peropyrene-N. The TCM reveal that both bonding and antibonding states involve the same set of primary transition orbitals, with in-phase orbital transition contributions dominating in the bonding state and out-of-phase contributions prevailing in the antibonding state. Notably, due to structural differences between monomers and incomplete resonance energy alignment, the antibonding resonance mode deviates from an ideal dark state, its non-zero oscillator strength gives rise to weak absorption intensity. For improved interpretation, diagrams of individual monomeric and total transition dipole moment contributions for both states are further presented in the insets of Figs. 3b-c (where red arrows represent monomeric contributions, green arrows denote total contributions, and arrow orientations indicate the transition dipole directions). These transition dipole moment contribution maps enable clear distinction between the photoexcitation characteristics of bonding and antibonding states. SPCA is employed to further analyze the excitation characteristics of the bonding and antibonding states. SPCA decomposes electronic excitation into contributions from individual electron-hole pair transitions, where each component is assigned a weight proportional to its significance in the overall excited state. Notably, only a few dominant single-particle electron-hole pair transitions contribute substantially to the excitation in the studied systems. In contrast, large quantum systems typically exhibit an increased number of dominant transition contributions with reduced individual weights. The SPCA results for the bonding and antibonding states of peropyrene-NC are graphically visualized on the electronic energy level (orbital contributions) diagrams of the system, as shown in Fig. 3d. Schematic diagrams of primary molecular orbitals are provided as insets, with the electron density in the molecular orbitals contributing to the transitions is predominantly localized within individual molecular units. Notably, both states involve the same set of major transition pathways (HOMO − 1→LUMO and HOMO→LUMO + 1), but the magnitudes of their contributions differ significantly. The bonding state is dominated by transitions localized on peropyrene (HOMO→LUMO + 1) and the antibonding state exhibits stronger contributions from peropyrene-N (HOMO − 1→LUMO). As a comparison, the optical properties of peropyrene-NO are analyzed, with relevant details provided in Figure S2 in the SM. For consistency, low-energy plasmonic excitations are designated as bonding states, and high-energy excitations as antibonding states. The insets of Figure S2a in the SM present the transition densities for these states, revealing that both plasmonic modes are dominated by single-molecule contributions, with negligible contributions from the other molecule. This asymmetry in transition density distribution clearly indicates weak intermolecular interactions, which are insufficient to induce characteristic plasmon hybridization effects. These observations are corroborated by the SPCA (Figure S2b in the SM) and TCM (Figure S2c-d). Moreover, atom-atom charge transfer analysis is performed for both the bonding and antibonding states of peropyrene-NC and peropyrene-NO, as shown in Fig. 4 . The atom-atom charge transfer matrices quantitatively depict inter-molecular and intra-molecular electron redistribution during excitation. Taking the bonding state of peropyrene-NC (Fig. 4 a) as an example, the heatmap is divided into four distinct regions. Regions 2 and 3 represent intramolecular electron redistribution within peropyrene and peropyrene-N, while regions 1 and 4 correspond to inter-molecular charge transfer from peropyrene-N to peropyrene and vice versa. As shown in Fig. 4 a-b, both the bonding and antibonding states of peropyrene-NC exhibit similar charge transfer behavior. Strong intramolecular redistribution occurs within the monomer that dominantly contributes to the primary molecular orbitals of the hybridization mode, with weaker intramolecular redistribution in the secondary contributor. Furthermore, significant inter-molecular charge transfer suggests efficient electronic coupling between the two monomers. These findings suggest that the plasmon hybridization in peropyrene-NC arises from synergistic interactions among all components, leading to a hybridized electronic structure. By contrast, peropyrene-NO displays fundamentally different behavior (Fig. 4 c-d) owing to weak or even negligible hybridization. Both states are dominated by intramolecular charge redistribution within the primary contributing molecule, with the negligible intermolecular charge transfer. This observation confirms the lack of strong plasmon interactions. 3.3 Tailoring Plasmon Hybridization by Charge Doping Previous studies have revealed that the plasmonic resonance peaks of both peropyrene and peropyrene-N exhibit a gradual red-shift with increasing charge doping concentration, ultimately approaching the resonance peak position of peropyrene-O. 39 Notably, the plasmonic resonance of peropyrene-O demonstrates remarkable stability to charge doping, maintaining its characteristic energy virtually unchanged across different charge doping levels. Thus, these findings suggest the intriguing possibility of modulating inter-molecular plasmon hybridization interactions in heterodimers by charge doping approaches, thereby offering new pathways for designing tunable molecular plasmonic nanostructures. We systematically characterize the absorption spectra and PI values for both peropyrene-NC under charge doping levels from − 2 to + 2 and for peropyrene-NO under doping from − 4 to + 4 (Figure S3-4 in the SM). Corresponding transition densities for bonding and antibonding states are illustrated in the insets. Comparative analysis reveals that in both positive and negative doping conditions, the maximum PI values occur under specific doping conditions (detailed data in Table S6-7 in the SM). To this end, we select the most representative cases for detailed examination: peropyrene-NC and peropyrene-NO under ± 2 charge doping. Figure 5 a-d present their absorption spectra and PI values, with insets illustrating the transition densities. Furthermore, Fig. 5 e depicts the ground-state atomic charge distribution within these heterodimers. The green values quantify the net atomic charge accumulated on peropyrene-N, revealing asymmetric redistribution due to structural non-equivalence and the distinct electronegativities of nitrogen and oxygen atoms dopants. Notably, this intrinsic asymmetry fundamentally governs their excitation behavior, as evidenced by the altered optical responses. Based on the analogous resonance peaks of peropyrene and peropyrene-N, coupled with their comparable responses to charge doping, the ground-state charge distribution within peropyrene-NC exerts a pronounced effect on its optical properties. As evident form the transition densities in Fig. 5 a-b under ± 2 charge doping, one molecule exhibits significantly stronger contributions than the other. This asymmetric contribution between two monomers suggests that the hybridization interaction in peropyrene-NC under ± 2 charge doping is weaker compared to its neutral state. This is primarily attributed to the asymmetric charge distribution. Specifically, as shown in Fig. 5 e, under − 2 charge doping, peropyrene-N carries a net charge of -1.0862 a.u., while peropyrene retains − 0.9138 a.u. Due to their responses to charge doping, peropyrene-N undergoes a more pronounced redshift compared to peropyrene, leading to an enhanced disparity in resonance peaks and consequently weakening the hybridization interaction within the heterodimer. Moreover, the greater redshift of peropyrene-N results in its dominant contribution to the bonding state, while the antibonding state is primarily from peropyrene. Similarly, under + 2 charge doping, peropyrene-N (0.8964 a.u.) carries a smaller net charge than peropyrene (1.1036 a.u.), resulting in a more significant redshift for peropyrene. This further diminishes the hybridization interaction in the heterodimer. Notably, the molecular contributions to the bonding and antibonding states are reversed compared to the − 2 charge doping case. In contrast to peropyrene-NC, peropyrene-NO exhibits distinct evolutionary trends in plasmon hybridization due to the relatively weaker influence of charge doping on peropyrene-O, as shown in Fig. 5 c-d. The transition densities reveal that under both − 2 and 2 charge doping conditions, the inter-molecular interaction strength in peropyrene-NO is significantly enhanced compared to its neutral state. The bonding state is predominantly contributed by peropyrene-O, while the antibonding state is primarily from peropyrene-N. Notably, further comparative analysis shows that the inter-molecular hybridization interaction is stronger under 2 charge doping than under − 2 charge doping. This can also be attributed to the charge distribution under ground-state condition (Fig. 5 e). Peropyrene-N carries a net charge of -0.5951 a.u. and 1.2687 a.u. under − 2 and 2 charge doping, respectively. This significantly higher charge in the latter case induces a more pronounced redshift in the plasmonic resonance peak of peropyrene-N compared to the − 2 charge doping case. Consequently, the resonance peaks of peropyrene-N and peropyrene-O become more closely aligned under + 2 charge doping, leading to stronger hybridization effects. Figure 6 – 7 present a systematic analysis of the bonding and antibonding states for peropyrene-NC and peropyrene-NO under charge doping conditions, including SPCA, molecular orbital diagrams, transition dipole moment contribution maps, and atom-atom charge transfer matrix heatmaps. For peropyrene-NC, SPCA (Fig. 6 a) reveals distinct orbital transition patterns under − 2 charge doping. The bonding state predominantly involves HOMO-2→LUMO, HOMO-1→LUMO and HOMO→LUMO + 4 transitions, while the antibonding state features HOMO-2→LUMO, HOMO-1→LUMO and HOMO→LUMO + 3 transitions. Under charge doping, electron density shifts between monomers, with the most pronounced changes in the HOMO and LUMO orbitals. This redistribution gives rise to distinct orbital transition patterns between the bonding and antibonding states, a feature not observed in the neutral state. Importantly, the bonding state is primarily associated with molecular orbitals dominated by peropyrene-N character, while the antibonding state is dominated by peropyrene-localized orbitals, consistent with transition density observations. The changes in molecular orbital electron density also influence the charge transfer characteristics of the bonding and antibonding states, as shown in Fig. 6 b-c. Strong electron redistribution occurs in the dominant orbital contributor, while weak electron redistribution is evident in the minor contributor, consistent with the charge transfer properties in the neutral state. Notably, charge transfer between the two monomers, with the magnitude of charge transfer is no longer approximately balanced but exhibits significant asymmetry. For the bonding state, the charge transfer from peropyrene-N to peropyrene is significantly greater than that from peropyrene to peropyrene-N, whereas the antibonding state exhibits the opposite charge transfer behavior. Additionally, the transition dipole moment contribution maps further confirm weaker plasmon hybridization interactions under − 2 charge doping compared to the neutral state. As illustrated in Fig. 6 d, SPCA analysis under 2 charge doping reveals that molecular orbital electron density evolution, similar to the − 2 charge doping case, leads to distinct transition compositions for the bonding and antibonding states. The bonding state is primarily contributed by HOMO-4→LUMO, HOMO→LUMO + 1, and HOMO→LUMO + 2 transitions, while the antibonding state is dominated by HOMO-3→LUMO, HOMO→LUMO + 1, and HOMO→LUMO + 2 transitions. Importantly, the bonding state transitions mainly originate from peropyren, whereas the antibonding state is dominated by peropyrene-N. The transition dipole moment contribution maps (Fig. 6 e-f) demonstrate that the plasmon hybridization interaction under 2 charge doping is significantly weaker than in the neutral state but comparable to that under − 2 charge doping. Similar to the − 2 charge doping condition, orbital electron density redistribution critically influences the charge transfer characteristics of the bonding and antibonding states. Pronounced electron reorganization occurs within the primary contribution monomer, while the secondary contributor exhibits only minor rearrangement. Moreover, the bonding state demonstrates pronounced charge from peropyrene-N to peropyrene, whereas the bonding state features a reversed peropyrene to peropyrene-N charge transfer pathway. Peropyrene-NO exhibits orbital electron density redistribution trends qualitatively analogous to peropyrene-NC, yet with markedly attenuated sensitivity to charge doping (Fig. 7 a and 7 d). SPCA analysis unequivocally indicates that under ± 2 charge doping, the bonding state transitions are exclusively dominated by peropyrene-O, while the antibonding states are dominated by peropyrene-N. This orbital selectivity directly dictates the charge transfer behavior (Figrue 7b-c and 7e-f), with the bonding states manifesting intra-molecular electron reorganization predominantly within peropyrene-O and the antibonding states corresponding to pronounced electron redistribution in peropyrene-N. Crucially, the transition dipole moment contribution maps reveal that although the inter-molecular hybridization in peropyrene-NO remains weak, it shows a doping-induced enhancement compared to the neutral state, with 2 charge doping case exhibiting stronger hybridization than under − 2 charge doping. Moreover, this enhanced hybridization gives rise to a distinct charge transfer pattern: 2 charge doping promotes charge transfer from peropyrene-N to peropyrene-O in both bonding and antibonding states, whereas − 2 charge doping induces a complete reversal, with peropyrene-O to peropyrene-N transfer prevails. The spatial distribution of transition density serves as a well-recognized metric for characterizing plasmonic oscillations. To this end, we integrate the transition density along the x direction for both peropyrene-NC and peropyrene-NO under ± 2 charge doping conditions, focusing on their bonding and antibonding states, as shown in Fig. 8 . For peropyrene-NC (Fig. 8 a-b), the neutral state exhibits nearly equal contributions from both constituent monomers to the transition density, hallmarking a typical close dipolar plasmon hybridization. Under charge doping, however, both bonding and antibonding states display asymmetric enhancement. One monomer’s plasmonic oscillation is dramatically amplified, while the other is strongly suppressed. This leads to weakened hybridization interaction and a transition from balanced hybrid plasmonic modes (the neutral state) to a single-molecule dominated plasmonic excitation (the charge doping states). Consequently, the PI value under charge doping exceeds that of the neutral state due to enhanced single-molecule oscillations. In stark contrast, peropyrene-NO (Fig. 8 c-d) shows that major contributing monomer oscillations (peropyrene-O for the bonding state and peropyrene-N for the antibonding state) are less sensitive to charge doping, while the minor contributor undergoes significant modulation, which is more pronounced under 2 charge doping than − 2 charge doping. This asymmetry thus explains why the PI value of peropyrene-NO increases under charge doping, with 2 charge doping exceeding − 2 charge doping, yet indicates that the system remains dominated by single-molecule plasmonic excitation, with relatively weak inter-molecular hybridization retained. 3.4 Tailoring Plasmon Hybrid States by Static Electric Field An external static electric field also serves as a method to tune the excitation properties of plasmons. While previous studies have demonstrated the influence of external static electric fields on the excitation properties of homodimeric nanosystems, 33 the effects on heterodimeric plasmonic systems remain largely unexplored. Herein, we investigate the modulation of plasmon hybridization in these heterodimers under external static electric fields ranging from − 0.004 a.u. to 0.004 a.u., with the electric field applied along the x direction. The absorption spectra and transition densities under these conditions are shown in Figure S5-6 in the SM, while the corresponding PI values are summarized in Table S8-9 in the SM. However, peropyrene-NO exhibits negligible field-induced hybridization changes, as evidenced by nearly additive single-molecule excitations in its absorption spectra and unaltered transition densities (Figure S5-6 in the SM). Thus, we focus our analysis on the more responsive peropyrene-NC. We employ external electric fields of -0.004 a.u. and 0.004 a.u. as representative cases for detailed analysis. As shown in Fig. 9 a-b, the absorption spectra, PI values and transition densities of the hybridized modes under these fields are presented. Figure 9 c illustrates the direction of the applied electric field and ground-state atomic charge distribution of peropyrene-NC. Under the − 0.004a.u. field, peropyrene-N carries a net charge of 0.0924 a.u., whereas under the 0.004 a.u. field, it bears a charge of -0.2390 a.u. Since the total system charge remains zero and both peropyrene and peropyrene-N exhibit comparable charge doping responses, the plasmonic resonance peaks of both components demonstrate comparable redshifts. Consequently, the plasmon hybridization interactions within peropyrene-NC remain largely unaltered. This conclusion is further substantiated by comparing the transition densities in the presence and absence of electric fields, which show no significant variations. Figure 9 d-f present the SPCA analysis, molecular orbital diagrams, atom-atom charge transfer matrix heatmaps and transition dipole moment contribution maps for peropyrene-NC under an external electric field of -0.004 a.u. The results show that the molecular orbital structure remains largely unperturbed under the applied − 0.004 a.u. external field (Fig. 9 d), with electron density distributions resembling those under the field-free condition and exhibiting pronounced localization in individual monomers. The bonding and antibonding states are predominantly characterized by HOMO-5→LUMO and HOMO→LUMO + 4 orbital transition, consistent with the field-free case, indicating two dominant orbital transition contributions. The bonding state is primarily associated with peropyrene contributions, while the antibonding state is dominated by peropyrene-N. Notably, the disparity between these two orbital transition contributions increases, suggesting a moderate reduction in heterodimer hybridization strength, as clearly shown in the transition dipole moment contribution maps of the hybridization modes (Fig. 9 e-f). This moderate influence of the − 0.004 a.u. external field on molecular orbitals leads to the charge transfer characteristics of the bonding and antibonding states largely resemble those under the field-free condition. However, the increased disparity in orbital transition contributions within the hybridization modes induces more pronounced electron redistribution in monomers with dominant orbital contributions, whereas secondary contributions exhibit weaker electron reorganization, compared to the field-free case. Applying 0.004 a.u. external electric field induces markedly different systematic responses, as detailed in Fig. 9 g-i. SPCA analysis reveals that the bonding and antibonding states are primarily contributed by HOMO-5→LUMO and HOMO→LUMO + 5 orbital transitions (Fig. 9 g). Importantly, these two transitions exhibit nearly equivalent contributions, indicating enhanced hybridization interactions in peropyrene-NC compared to the field-free condition. This finding is further corroborated by the transition dipole moment contribution distributions (Fig. 9 h-i), where molecular contributions to bonding and antibonding states approach parity. Particularly significant is the near-zero transition dipole moment in the antibonding state, achieving an ideal dark plasmonic excitation mode. The 0.004 a.u. external field substantially modifies the electron density distributions of molecular orbitals, with the most pronounced effects in HOMO and LUMO orbitals. The electron density evolves from monomer-localized to delocalized distributions spanning both molecular units. This redistribution of orbital electron density further modulates the charge transfer of the hybridization modes. The charge transfer characteristics of bonding and antibonding states exhibit high consistency, attributed to the similar magnitudes of dominant orbital transitions and their contributions. Significantly, four distinct charge transfer processes emerge with nearly equivalent magnitudes: intra-molecular electron redistribution within peropyrene, intra-molecular electron reorganization within peropyrene-N, electron transfer from peropyrene-N to peropyrene, and electron transfer from peropyrene to peropyrene-N. We perform an integrated analysis of the transition density along the x direction for both bonding and antibonding states of peropyrene-NC under various external electric fields, as illustrated in Fig. 10 . Under − 0.004 a.u. external electric field, the plasmonic oscillation in dominant monomers (peropyrene for the bonding state and peropyrene-N for the antibonding state) is moderately enhanced, while that in their counterparts is relatively suppressed, leading to weakened plasmon hybridization interactions. By contrast, the 0.004 a.u. external electric field renders plasmonic oscillation intensities of both monomers in the hybridized modes more comparable, thereby partially enhancing the plasmon hybridization characteristics of the heterodimer. This is further confirmed by the evolution of PI values for peropyrene-NC hybridized modes with applied electric field strength. As shown in Figure S7 in the SM, when the external field increases from − 0.004 a.u. to 0.004 a.u., both bonding and antibonding states exhibit progressively increasing PI values, clearly indicating the continuous enhancement of the plasmonic excitation characteristics. Our investigation reveals that both charge doping and external static electric fields can effectively tailor plasmon hybridization interactions in heterodimers, albeit with distinct degrees of control. The charge doping approach demonstrates a robust capability to manipulate the plasmon hybridization modes, enabling a progressive transition from the initial hybridized plasmonic state to a single-molecule dominated plasmonic excitation mode. By contrast, external electric field modulation primarily operates within the framework of plasmon hybridization, fine-tuning the interaction strength between the heterodimer components to either approach or deviate from the ideal plasmon hybridization state. It is worth that the theoretical configurations proposed in this study are well-supported by recent experimental advances in supramolecular electrons. Specifically, experimental studies have successfully constructed stable dimer structures comprising two molecules using the scanning tunneling microscope-based break junction technique. 62 – 64 Furthermore, mechanisms such as electric field-induced assembly 65 and vibration-assisted transport 66 have been directly observed. These experimental advances provide experimental feasibility for the theoretical mechanisms discussed in this work. 4. Conclusions In this study, we investigate plasmon hybridization tailoring in peropyrene heterodimers using LR-TDDFT calculations with various analytical methods. Neutral peropyrene-NC exhibits strong plasmon hybridization with bonding and antibonding modes showing similar charge transfer characteristics within molecules, while maintaining equivalent intermolecular charge transfer magnitudes. In contrast, neutral peropyrene-NO shows almost no hybridization effects, displaying only single-molecule dominated excitations with negligible inter-molecular charge transfer. Charge doping effectively modulates these hybridization effects-attenuating strong hybridization in peropyrene-NC due to differential molecular responses to doping, while inducing previously absent hybridization in peropyrene-NO with directional electron transfer that reverses between negative and positive doping. Static electric fields provide precise control of hybridization strength in peropyrene-NC: negative fields (-0.004 a.u.) weaken hybridization by enhancing primary molecular contributions while reducing secondary contributions and inter-molecular transfer, whereas positive fields (0.004 a.u.) drive the system toward ideal hybridization with the antibonding transition dipole approaching zero and perfectly symmetric charge transfer. However, static fields show limited efficacy in inducing hybridization in peropyrene-NO. Our results indicate that combining charge doping and static electric fields can modulate molecular plasmon hybridization at the molecular scale. These observations contribute to the understanding of molecular plasmons and may be relevant for future molecular plasmonic devices requiring tailored optical responses. Declarations Authors contribution Y. F conceived the idea and directed the project. H. L and N. G did DFT and TDDFT calculations. H. L and Y. F analyzed the data and wrote the manuscript. All the authors revised the manuscript. Funding This research was supported by the National Natural Science Foundation of China (Grant No. 12274054, 12074054). Conflicts of interest The authors declare no competing financial interest. Availability of data and material The data and material that support the findings of this study are available from the corresponding author upon reasonable request. 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Supplementary Files SIManuscript.docx Cite Share Download PDF Status: Published Journal Publication published 23 Apr, 2026 Read the published version in Plasmonics → Version 1 posted Editorial decision: Revision requested 09 Apr, 2026 Reviews received at journal 08 Apr, 2026 Reviewers agreed at journal 06 Apr, 2026 Reviewers invited by journal 30 Mar, 2026 Editor assigned by journal 26 Mar, 2026 Submission checks completed at journal 26 Mar, 2026 First submitted to journal 26 Mar, 2026 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. 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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-9229438","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":615486725,"identity":"7604d785-9430-41e0-b297-545d01a036ac","order_by":0,"name":"Haoran Liu","email":"","orcid":"","institution":"Dalian University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Haoran","middleName":"","lastName":"Liu","suffix":""},{"id":615486727,"identity":"54e6e0a4-de67-454e-a294-fb2eb481a103","order_by":1,"name":"Nan Gao","email":"","orcid":"","institution":"Dalian University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Nan","middleName":"","lastName":"Gao","suffix":""},{"id":615486728,"identity":"4983150b-f075-400c-b0e8-9b76e863d810","order_by":2,"name":"Yongqi Chen","email":"","orcid":"","institution":"Dalian University of Technology","correspondingAuthor":false,"prefix":"","firstName":"Yongqi","middleName":"","lastName":"Chen","suffix":""},{"id":615486730,"identity":"277a4973-ea4e-454a-ace1-b47ab16677b8","order_by":3,"name":"Yurui Fang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAzklEQVRIiWNgGAWjYFACxgdAwoaxD8xhI0oLswGQSGNsY2AmTcthErQY3D7M+Lng13nZNon8Awwfyg4z8M9uIKDlXDKz9My+28ZtEskMjDPOHWaQuHOAgJYz/AekeXtuJ4K0MPO2HWYwkEggpIWZ+TdvzzmIlr9EamGT5vlxAKKFkRgtkkAt1rwNycZtPI8NDvacS+eRuEFACx/QYbd5/tjJ9rMnPnzwo8xajn8GAS0KB4AEMFLAAMTmwa8eCOQbQOQfgupGwSgYBaNgJAMAk1ZAHYXxVqYAAAAASUVORK5CYII=","orcid":"","institution":"Dalian University of Technology","correspondingAuthor":true,"prefix":"","firstName":"Yurui","middleName":"","lastName":"Fang","suffix":""}],"badges":[],"createdAt":"2026-03-26 05:23:59","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9229438/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9229438/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11468-026-03361-9","type":"published","date":"2026-04-23T15:58:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":106093436,"identity":"f763ec19-a849-4252-85de-96f3fcdb0b9c","added_by":"auto","created_at":"2026-04-03 11:37:21","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":791729,"visible":true,"origin":"","legend":"\u003cp\u003eSpectroscopic characterization and plasmonic properties of peropyrene and its derivatives. (a-c) Absorption spectra and corresponding PI values for (a) peropyrene, (b) peropyrene-N, and (c) peropyrene-O. Red arrows indicate longitudinal dipole plasmonic resonance modes corresponding to S\u003csub\u003e1\u003c/sub\u003e state. Optimized molecular structures are shown in the insets, where atomic species are color-coded as displayed in the red box. (d-f) TCMs for the S\u003csub\u003e1\u003c/sub\u003e state of (d) peropyrene, (e) peropyrene-N, and (f) peropyrene-O, showing orbital transition weights with red signifying positive contributions and blue indicating negative contributions. The dashed line is included to represent a constant excitation energy level. The \u003cem\u003ef \u003c/em\u003evalues represent the oscillator strength. The insets show the transition densities.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/61ee0287212dc4ad0fb3c3e1.png"},{"id":106093415,"identity":"b7e7e5b8-4d85-41ab-8e7c-8925d8a0d308","added_by":"auto","created_at":"2026-04-03 11:37:16","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":511946,"visible":true,"origin":"","legend":"\u003cp\u003eStructural characteristics and spectroscopic analysis of substituted peropyrene derivatives. (a-b) Geometric structure diagrams for (a) peropyrene-NC and (b) peropyrene-NO. (c-d) Absorption spectra and corresponding PI values for (c) peropyrene-NC and (d) peropyrene-NO. The dashed lines represent the total absorption spectra. The solid lines represent the two distinct plasmonic excitation modes, where the S\u003csub\u003e4\u003c/sub\u003e state absorption in (c) is magnified by a factor of 50 for clearer comparison.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/ca7982ef37eb8476724f8ee5.png"},{"id":106401754,"identity":"8da0f3c8-0397-4738-8b13-9c1ed73b18d4","added_by":"auto","created_at":"2026-04-08 09:09:30","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1018103,"visible":true,"origin":"","legend":"\u003cp\u003ePlasmon hybridization mechanism and orbital analysis in substituted peropyrene-NC. (a) Schematic diagram of plasmon hybridization in peropyrene-NC, including the transition densities for both monomeric and dimeric plasmonic excitation modes. The red numerical values indicate the energy deviations of the monomeric resonance relative to the corresponding hybridization modes. The inset in the lower-right corner (green dashed box) displays the ground-state atomic charge distribution, with the green value indicating the net atomic charge accumulated on peropyrene-N. (b-c) TCMs for the (b) bonding state and (c) antibonding state of peropyrene-NC. The insets depict the transition dipole moment contribution maps for the respective hybridization states, with red arrows represent monomeric contributions, green arrows denote total contributions, and arrow orientations indicate the transition dipole directions. (d) SPCA of bonding and antibonding states for peropyrene-NC. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-1, HOMO, LUMO, LUMO+1). Green arrows highlight the dominant orbital transitions involved in the excited states, and blue numbers indicate their relative contributions.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/294e8bdc72b0513d189b2481.png"},{"id":106093412,"identity":"33ae3026-0378-4d06-baa3-c362b4a33da7","added_by":"auto","created_at":"2026-04-03 11:37:16","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":956859,"visible":true,"origin":"","legend":"\u003cp\u003eCharge transfer analysis in hybridized plasmonic states of substituted peropyrene derivatives. (a-b) Atom-atom charge transfer matrix heatmaps for the (a) bonding state and (b) antibonding state of peropyrene-NC. (c-d) Atom-atom charge transfer matrix heatmaps for the (c) bonding state and (d) antibonding state of peropyrene-NO.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/0d8927c32a953b01dfc6a185.png"},{"id":106093321,"identity":"c06db484-735b-4500-aad9-0dc6e8712f55","added_by":"auto","created_at":"2026-04-03 11:36:44","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":897773,"visible":true,"origin":"","legend":"\u003cp\u003eEffects of charge doping on plasmonic properties of substituted peropyrene derivatives. (a-b) Absorption spectra and corresponding PI values of peropyrene-NC under (a) -2 charge doping and (b) 2 charge doping. (c-d) Absorption spectra and corresponding PI values of peropyrene-NO under (c) -2 charge doping and (d) 2 charge doping. The insets display the transition densities for the bonding and antibonding states. (e) The ground-state atomic charge distribution corresponding to the four previously discussed doping configurations. The green values quantify the net atomic charge accumulated on peropyrene-N.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/67e0901107d0e3c4f0e0203e.png"},{"id":106093210,"identity":"8b2a0bad-2ea1-4043-a382-b7567d12f3e5","added_by":"auto","created_at":"2026-04-03 11:36:01","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":988227,"visible":true,"origin":"","legend":"\u003cp\u003eOrbital analysis and charge transfer characteristics of peropyrene-NC under charge doping conditions. (a) SPCA of bonding and antibonding states for peropyrene-NC under -2 charge doping. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-2, HOMO-1, HOMO, LUMO, LUMO+3, LUMO+4). (b-c) Atom-atom charge transfer matrix heatmaps and transition dipole moment contribution maps for the (b) bonding state and (c) antibonding state of peropyrene-NC under -2 charge doping. (d) SPCA of bonding and antibonding states for peropyrene-NC under 2 charge doping. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-4, HOMO-3, HOMO, LUMO, LUMO+1, LUMO+2). (e-f) Atom-atom charge transfer matrix heatmaps and transition dipole moment contribution maps for the (e) bonding state and (f) antibonding state of peropyrene-NC under 2 charge doping.\u003c/p\u003e","description":"","filename":"floatimage6.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/f6b480c69ace347eebbe3f57.png"},{"id":105933115,"identity":"a3e48316-d80a-4db0-a539-c8362e43bf58","added_by":"auto","created_at":"2026-04-01 14:31:44","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":1005679,"visible":true,"origin":"","legend":"\u003cp\u003eOrbital analysis and charge transfer characteristics of peropyrene-NO under charge doping conditions. (a) SPCA of bonding and antibonding states for peropyrene-NO under -2 charge doping. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-2, HOMO-1, HOMO, LUMO, LUMO+2, LUMO+4). (b-c) Atom-atom charge transfer matrix heatmaps and transition dipole moment contribution maps for the (b) bonding state and (c) antibonding state of peropyrene-NO under -2 charge doping. (d) SPCA of bonding and antibonding states for peropyrene-NO under 2 charge doping. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-10, HOMO-8, HOMO, LUMO, LUMO+1, LUMO+2). (e-f) Atom-atom charge transfer matrix heatmaps and transition dipole moment contribution maps for the (e) bonding state and (f) antibonding state of peropyrene-NO under 2 charge doping.\u003c/p\u003e","description":"","filename":"floatimage7.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/ad91d020b0153e97cbac4411.png"},{"id":106093770,"identity":"d1961490-43ee-4322-b3fb-cb5ab4fcbd86","added_by":"auto","created_at":"2026-04-03 11:39:04","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":868196,"visible":true,"origin":"","legend":"\u003cp\u003eSpatial analysis of transition density distributions in charge-doped peropyrene derivatives. (a-b) Transition density integral curves along the \u003cem\u003ex\u003c/em\u003edirection for the (a) bonding state and (b) antibonding state of peropyrene-NC under ±2 charge doping. (c-d) Transition density integral curves along the \u003cem\u003ex\u003c/em\u003edirection for the (c) bonding state and (d) antibonding state of peropyrene-NO under ±2 charge doping.\u003c/p\u003e","description":"","filename":"floatimage8.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/1eedf6367addd0a5d105dbef.png"},{"id":106093240,"identity":"36339c94-f36e-48ff-80f8-8bcaeaacd1d3","added_by":"auto","created_at":"2026-04-03 11:36:15","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":1472410,"visible":true,"origin":"","legend":"\u003cp\u003eElectric field-induced tailoring of plasmon resonance in peropyrene-NC. (a-b) Absorption spectra and corresponding PI values for peropyrene-NC under static electric field of (a) -0.004 a.u. and (b) 0.004 a.u. (c) The ground-state atomic charge distribution for the two electric field configurations. The green values quantify the net atomic charge accumulated on peropyrene-N. The purple arrow indicates the external electric field direction. (d) SPCA of bonding and antibonding states for peropyrene-NC under static electric field of -0.004 a.u. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-5, HOMO, LUMO, LUMO+4). (e-f) Atom-atom charge transfer matrix heatmaps and transition dipole moment contribution maps of the (e) bonding state and (f) antibonding state under static electric field of -0.004 a.u. (g) SPCA of bonding and antibonding states for peropyrene-NC under static electric field of 0.004 a.u. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-5, HOMO, LUMO, LUMO+5). (h-i) Atom-atom charge transfer matrix heatmaps and transition dipole moment contribution maps of the (e) bonding state and (f) antibonding state for peropyrene-NC under static electric field of 0.004 a.u.\u003c/p\u003e","description":"","filename":"floatimage9.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/379b35ed88edd03547faefaf.png"},{"id":105933122,"identity":"f4946e62-efe5-4805-9b36-4182c1a8ba73","added_by":"auto","created_at":"2026-04-01 14:31:44","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":456292,"visible":true,"origin":"","legend":"\u003cp\u003eSpatial transition density analysis of peropyrene-NC under opposing electric field configurations. (a-b) Transition density integral curves along the \u003cem\u003ex\u003c/em\u003e direction of the (a) bonding state and (b) antibonding state for peropyrene-NC under static electric field of -0.004 a.u. and 0.004 a.u.\u003c/p\u003e","description":"","filename":"floatimage10.png","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/ba6b1ed9a7670434c8302d29.png"},{"id":107927889,"identity":"335a3796-bba2-4a9b-af6a-3185da0e1175","added_by":"auto","created_at":"2026-04-27 16:05:52","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":9258110,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/5ebd258c-07f2-4db0-855c-9a44d82a440d.pdf"},{"id":106093416,"identity":"6189f114-1d79-4eb6-8cc1-1fe3a79116a9","added_by":"auto","created_at":"2026-04-03 11:37:17","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":3389199,"visible":true,"origin":"","legend":"","description":"","filename":"SIManuscript.docx","url":"https://assets-eu.researchsquare.com/files/rs-9229438/v1/fc3db07710ca46a1896838f1.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Tailoring Plasmon Hybrid States in Peropyrene Heterodimers by Charge Doping and Static Electric Field","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003ePlasmon hybridization, as a crucial analyzing method in nanophotonics, has attracted significant attention in recent years due to its unique role in light-matter interactions.\u003csup\u003e\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u003c/sup\u003e Traditional plasmonic studies on metallic nanoparticles have established a relatively complete theoretical framework, with the plasmon hybridization theory initially proposed by Nordlander et al. in 2003.\u003csup\u003e\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e This theory successfully explains the coupling mechanism of surface plasmonic resonances (SPRs) in metallic nanostructures and provides an intuitive description of the interactions between different plasmonic excitations, laying an important foundation for the design of nanophotonic devices.\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u003c/sup\u003e Although this theory has achieved notable success in studying macroscopic nanostructures, as the system decreases to molecular scales, quantum effects become increasingly prominent,\u003csup\u003e10\u0026ndash;13\u003c/sup\u003e posing new challenges for a deeper understanding of the fundamental physical mechanisms of plasmons.\u003c/p\u003e \u003cp\u003eAs an ab initio quantum mechanical approach, time-dependent density functional theory (TDDFT)\u003csup\u003e\u003cspan additionalcitationids=\"CR15\" citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e provides a rigorous theoretical framework for characterizing plasmonic excitation properties at the molecular scale.\u003csup\u003e\u003cspan additionalcitationids=\"CR18 CR19 CR20 CR21 CR22 CR23 CR24 CR25 CR26\" citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e In recent years, TDDFT and its approximate methods have been increasingly employed to investigate the optical properties of metallic nanocluster dimers.\u003csup\u003e\u003cspan additionalcitationids=\"CR29 CR30 CR31 CR32 CR33\" citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u003c/sup\u003e However, research on plasmon hybridization and its tunability in molecular scale systems remains relatively scarce, despite their established ability to support plasmonic excitations.\u003csup\u003e\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e, \u003cspan additionalcitationids=\"CR35\" citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e In contrast to conventional metallic nanostructures, conjugated molecular systems (e.g., polycyclic aromatic hydrocarbons, alkene chains) offer unique advantages. Their structural precision enables angstrom-scale control over plasmonic responses, and rich chemical modification strategies provide versatile pathways for dynamically tuning plasmonic strategies. These characteristics endow molecular plasmonic systems with promising potential for applications in nanophotonic device development.\u003csup\u003e\u003cspan additionalcitationids=\"CR37\" citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e\u003c/p\u003e \u003cp\u003eAs a prototypical class of molecular plasmonic systems, peropyrene and its derivatives have been studied, with their optical properties comprehensively characterized in prior works.\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e Building upon this foundation, the present work investigates the modulation mechanisms of plasmon hybridization in peropyrene heterodimers through charge doping and static electric field manipulation. Using linear response TDDFT (LR-TDDFT) calculations complemented by plasmonicity index (PI),\u003csup\u003e40\u003c/sup\u003e generalized plasmonicity index (GPI),\u003csup\u003e41\u003c/sup\u003e transition contribution map (TCM),\u003csup\u003e42\u0026ndash;45\u003c/sup\u003e single-particle component analysis (SPCA)\u003csup\u003e\u003cspan additionalcitationids=\"CR47 CR48\" citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e and charge transfer characterization, we investigate the optical responses and hybridization characteristics of two distinct heterodimer configurations. When constituent monomers exhibit proximal plasmonic resonance energies, the heterodimer demonstrates remarkable hybridization phenomena, manifesting as characteristic bonding and antibonding excitation mode. Comparative analysis of modulation approaches shows that the charge doping exerts more pronounced effects on hybridization tuning than external static electric field. Notably, through deliberate design of heterodimer composition, charge doping can activate hybridization effects that are absent in neutral states. These findings characterize plasmon hybridization mechanisms at the molecular scale, hinting at possibilities for future dynamically tunable nanophotonic devices based on molecular plasmons.\u003c/p\u003e"},{"header":"2. Methods","content":"\u003cp\u003eAll LR-TDDFT calculations based on the Casida\u0026rsquo;s equation solved in the basis of Kohn-Sham particle-hole transitions are performed using the Gaussian 16 software.\u003csup\u003e\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u003c/sup\u003e The study focuses on two distinct heterodimer configurations, one consists of peropyrene-N (modified with nitrogen atoms) and peropyrene arranged along the \u003cem\u003ex\u003c/em\u003e-axis (peropyrene-NC), and the other comprises of peropyrene-N and peropyrene-O (modified with nitrogen and oxygen atoms) aligned along with \u003cem\u003ex\u003c/em\u003e-axis (peropyrene-NO). The initial monomer geometries are adopted from our previous work.\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e All heterodimer configurations, including those under charge doping and external static electric field, are fully optimized to their equilibrium structures. Consequently, inter-molecular spacing varies slightly across different conditions, this parameter is not investigated systematically in the current study.\u003c/p\u003e \u003cp\u003eConsistent with our prior research and to ensure balanced accuracy between plasmonic excitation characterization and computational feasibility, we employ the TPSSH exchange-correlation functional\u003csup\u003e\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e, \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u003c/sup\u003e with the 6-311G(d,p) basis sets\u003csup\u003e\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e\u003c/sup\u003e and the DFT-D3(BJ) dispersion correction\u003csup\u003e\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e, \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e\u003c/sup\u003e for all calculations, including geometric optimization, ground-state electronic structure, and absorption spectra simulations. To achieve a reliable description of excited states, we include all orbital transition contributions with an oscillator strength threshold of 10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e. Spectral broadening is modeled using Gaussian damping with a width parameter of 0.20 eV. For charge doping investigations, we characterize the optical properties of peropyrene-NC for charge states between \u0026minus;\u0026thinsp;2 and +\u0026thinsp;2, whereas peropyrene-NO is examined over a broader range (\u0026minus;\u0026thinsp;4 to +\u0026thinsp;4). In the case of static electric field effects, both heterodimers are analyzed under field strengths from \u0026minus;\u0026thinsp;0.004 a.u. to +\u0026thinsp;0.004 a.u. applied along the \u003cem\u003ex\u003c/em\u003e direction. Computational settings for charged and field-modulated systems remain identical to those of the neutral state calculations.\u003c/p\u003e \u003cp\u003ePlasmonic excitation characteristics are evaluated using PI, GPI, TCM, SPCA analyses, as detailed in earlier publications.\u003csup\u003e\u003cspan additionalcitationids=\"CR40 CR41 CR42 CR43 CR44 CR45 CR46 CR47 CR48\" citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e\u003c/sup\u003e Atomic charge distributions are quantified using the atomic dipole moment corrected Hirshfeld (ADCH) population method,\u003csup\u003e56\u003c/sup\u003e chosen for its superior general applicability and physical soundness.\u003csup\u003e\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e\u003c/sup\u003e Concurrently, the interfragment charge transfer (IFCT)\u003csup\u003e\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e\u003c/sup\u003e based on the default Mulliken-like partition, is employed to quantify electron redistribution (both between and within individual monomers), with each molecular unit treated as a sepa rate fragment. All post-processing of ground-state electron structures, excited-state properties, ADCH and IFCT analyses are performed using the wave function analysis software Multiwfn 3.8(dev).\u003csup\u003e\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e, \u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e\u003c/sup\u003e For visualization, molecular structures and date plots are rendered using VMD\u003csup\u003e\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e\u003c/sup\u003e and VESTA\u003csup\u003e\u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e\u003c/sup\u003e software.\u003c/p\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Single-Molecule Plasmonic Excitations\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eBuilding upon our systematic investigations of plasmonic excitations in peropyrene and its derivatives (peropyrene-N and peropyrene-O),\u003csup\u003e39\u003c/sup\u003e we establish monomeric optical properties as the foundation for heterodimer studies. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea-c present the absorption spectra, PI values, and optimized structures of these three systems. To further strengthen the reliability of our findings, we calculate the GPI values for the first ten excited states. The PI and GPI values exhibit highly consistent evolutionary trends (see Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e-3 in the Supplemental Material (SM)), reinforcing the robustness of our results. Though minor spectral blue-shifts are observed due to differences in exchange-correlation functionals (see Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e in the SM), the overall spectral evolution remained consistent, validating our computational approach. Additionally, Figure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003ed in the SM demonstrates that subtle geometric variations in peropyrene-N across different heterodimer configurations do not significantly alter its absorption characteristics. Hence, we select peropyrene-N monomer form peropyrene-NC heterodimer structure for further single-molecule analysis.\u003c/p\u003e \u003cp\u003eTCM provides an effective framework for characterizing plasmonic excitations. Thus, we compute TCM and transition densities (see Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed-f) for the first excited state S\u003csub\u003e1\u003c/sub\u003e (S\u003csub\u003e0\u003c/sub\u003e\u0026rarr;S\u003csub\u003e1\u003c/sub\u003e), where the PI values peak. The TCM unambiguously reveals the plasmonic nature of the excitations, while the transition densities confirm a longitudinal dipole plasmonic resonance mode, aligning with prior theoretical findings. Due to the small molecular size, the Kohn-Sham states exhibit discrete energy levels, leading to relatively weak collective excitations, as evidenced by the TCM wherein the plasmonic excitations predominantly arise from the HOMO\u0026rarr;LUMO transition.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Plasmon Hybridization Properties of Heterodimers\u003c/h2\u003e \u003cp\u003eFurthermore, we conduct an analysis on the excitation characteristics of peropyrene-NC heterodimer composed of peropyrene-N and peropyrene, as well as peropyrene-NO heterodimer formed by peropyrene-N and peropyrene-O. During this process, we only consider the peropyrene heterodimers placed along the \u003cem\u003ex\u003c/em\u003e-axis, and the specific geometric structure diagrams can be referred to in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea-b. It should be noted that since we directly perform geometric optimization on the heterodimer configurations, the molecular spacing in the two heterodimers are not the same. Therefore, the influence of inter-molecular spacing is not analyzed in the current investigation.\u003c/p\u003e \u003cp\u003eThrough computational analysis, we obtain the total absorption spectra (dashed line) and corresponding PI values for the heterodimers, as presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec-d. In addition, we further provide the excitation energies, oscillator strengths, and GPI values corresponding to the first fifteen excited states, the relevant data are listed in Table S4-5 in the SM. The results demonstrate a strong correlation between PI and GPI values evolution trends, with both heterodimers exhibiting two distinct plasmonic excitation modes within specific spectral ranges. To further analyze these modes, we extract the absorption spectra corresponding to the plasmonic excitations, which are shown as solid lines in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec-d. In previous research work, it has been found that for the structures composed of molecular systems supporting plasmonic excitation modes, their plasmon responses can be effectively described using the plasmon hybridization model. Therefore, our subsequent analyses employ this framework to investigate the observed plasmonic behavior. The hybridization effect is predominantly governed by the intermolecular interaction strength and the resonant energy alignment of the initial plasmonic modes. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea-c, while peropyrene and peropyrene-N exhibit colsely matched plasmonic resonance energies, peropyrene-O demonstrates a pronounced energetic detuning. This energetic mismatch results in significantly plasmon interaction in peropyrene-NC compared to peropyrene-NO, leading to distinct hybridization phenomena exclusively observed in peropyrene-NC.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eWe firstly analyze the excitation characteristics of peropyrene-NC. Figure\u0026nbsp;3a presents a schematic diagram of the plasmon hybridization modes in peropyrene-NC, comparing the transition densities of plasmonic excitation modes between monomeric and dimeric structures. The transition densities clearly identify low-energy bonding and high-energy antibonding plasmonic resonance modes formed by hybridization. Quantitative analysis shows that the bonding state exhibits a 0.031 eV energy shift relative to peropyrene\u0026rsquo;s isolated resonance, while the antibonding state shows a 0.019 eV energy shift relative to peropyrene-N\u0026rsquo;s resonance. These substantial energetic perturbations unambiguously confirm the presence of strong intermolecular interactions. Owing to the short interdimer spacing and electronic perturbation induced by nitrogen and oxygen atoms doping, charge transfer occurs in the dimers under equilibrium conditions. Thus, we calculate the charge distribution of peropyrene-NC, as shown in the lower-right inset of Fig.\u0026nbsp;3a, where blue represents negative charge and red represents positive charge. Quantitative analysis of total charge on peropyrene-N (indicated below the inset) confirms a net charge of 0.0604 a.u., demonstrating weak intermolecular charge transfer. Such minute charge quantities are inaccessible in monomeric structure calculations, potentially introducing unavoidable errors into the actual analysis.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure 3. Plasmon hybridization mechanism and orbital analysis in substituted peropyrene-NC. (a) Schematic diagram of plasmon hybridization in peropyrene-NC, including the transition densities for both monomeric and dimeric plasmonic excitation modes. The red numerical values indicate the energy deviations of the monomeric resonance relative to the corresponding hybridization modes. The inset in the lower-right corner (green dashed box) displays the ground-state atomic charge distribution, with the green value indicating the net atomic charge accumulated on peropyrene-N. (b-c) TCMs for the (b) bonding state and (c) antibonding state of peropyrene-NC. The insets depict the transition dipole moment contribution maps for the respective hybridization states, with red arrows represent monomeric contributions, green arrows denote total contributions, and arrow orientations indicate the transition dipole directions. (d) SPCA of bonding and antibonding states for peropyrene-NC. The dashed boxes show molecular orbital diagrams corresponding to the energy levels (bottom to top: HOMO-1, HOMO, LUMO, LUMO\u0026thinsp;+\u0026thinsp;1). Green arrows highlight the dominant orbital transitions involved in the excited states, and blue numbers indicate their relative contributions.\u003c/p\u003e \u003cp\u003eFigures 3b-c show the TCM and density of states (DOS) for the bonding and antibonding states of peropyrene-NC, where the yellow region in the DOS plot signifies the contribution from peropyrene-N. The TCM reveal that both bonding and antibonding states involve the same set of primary transition orbitals, with in-phase orbital transition contributions dominating in the bonding state and out-of-phase contributions prevailing in the antibonding state. Notably, due to structural differences between monomers and incomplete resonance energy alignment, the antibonding resonance mode deviates from an ideal dark state, its non-zero oscillator strength gives rise to weak absorption intensity. For improved interpretation, diagrams of individual monomeric and total transition dipole moment contributions for both states are further presented in the insets of Figs.\u0026nbsp;3b-c (where red arrows represent monomeric contributions, green arrows denote total contributions, and arrow orientations indicate the transition dipole directions). These transition dipole moment contribution maps enable clear distinction between the photoexcitation characteristics of bonding and antibonding states.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eSPCA is employed to further analyze the excitation characteristics of the bonding and antibonding states. SPCA decomposes electronic excitation into contributions from individual electron-hole pair transitions, where each component is assigned a weight proportional to its significance in the overall excited state. Notably, only a few dominant single-particle electron-hole pair transitions contribute substantially to the excitation in the studied systems. In contrast, large quantum systems typically exhibit an increased number of dominant transition contributions with reduced individual weights. The SPCA results for the bonding and antibonding states of peropyrene-NC are graphically visualized on the electronic energy level (orbital contributions) diagrams of the system, as shown in Fig.\u0026nbsp;3d. Schematic diagrams of primary molecular orbitals are provided as insets, with the electron density in the molecular orbitals contributing to the transitions is predominantly localized within individual molecular units. Notably, both states involve the same set of major transition pathways (HOMO\u0026thinsp;\u0026minus;\u0026thinsp;1\u0026rarr;LUMO and HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;1), but the magnitudes of their contributions differ significantly. The bonding state is dominated by transitions localized on peropyrene (HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;1) and the antibonding state exhibits stronger contributions from peropyrene-N (HOMO\u0026thinsp;\u0026minus;\u0026thinsp;1\u0026rarr;LUMO).\u003c/p\u003e \u003cp\u003eAs a comparison, the optical properties of peropyrene-NO are analyzed, with relevant details provided in Figure S2 in the SM. For consistency, low-energy plasmonic excitations are designated as bonding states, and high-energy excitations as antibonding states. The insets of Figure S2a in the SM present the transition densities for these states, revealing that both plasmonic modes are dominated by single-molecule contributions, with negligible contributions from the other molecule. This asymmetry in transition density distribution clearly indicates weak intermolecular interactions, which are insufficient to induce characteristic plasmon hybridization effects. These observations are corroborated by the SPCA (Figure S2b in the SM) and TCM (Figure S2c-d).\u003c/p\u003e \u003cp\u003eMoreover, atom-atom charge transfer analysis is performed for both the bonding and antibonding states of peropyrene-NC and peropyrene-NO, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The atom-atom charge transfer matrices quantitatively depict inter-molecular and intra-molecular electron redistribution during excitation. Taking the bonding state of peropyrene-NC (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003ea) as an example, the heatmap is divided into four distinct regions. Regions 2 and 3 represent intramolecular electron redistribution within peropyrene and peropyrene-N, while regions 1 and 4 correspond to inter-molecular charge transfer from peropyrene-N to peropyrene and vice versa. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003ea-b, both the bonding and antibonding states of peropyrene-NC exhibit similar charge transfer behavior. Strong intramolecular redistribution occurs within the monomer that dominantly contributes to the primary molecular orbitals of the hybridization mode, with weaker intramolecular redistribution in the secondary contributor. Furthermore, significant inter-molecular charge transfer suggests efficient electronic coupling between the two monomers. These findings suggest that the plasmon hybridization in peropyrene-NC arises from synergistic interactions among all components, leading to a hybridized electronic structure. By contrast, peropyrene-NO displays fundamentally different behavior (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e4\u003c/span\u003ec-d) owing to weak or even negligible hybridization. Both states are dominated by intramolecular charge redistribution within the primary contributing molecule, with the negligible intermolecular charge transfer. This observation confirms the lack of strong plasmon interactions.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Tailoring Plasmon Hybridization by Charge Doping\u003c/h2\u003e \u003cp\u003ePrevious studies have revealed that the plasmonic resonance peaks of both peropyrene and peropyrene-N exhibit a gradual red-shift with increasing charge doping concentration, ultimately approaching the resonance peak position of peropyrene-O.\u003csup\u003e39\u003c/sup\u003e Notably, the plasmonic resonance of peropyrene-O demonstrates remarkable stability to charge doping, maintaining its characteristic energy virtually unchanged across different charge doping levels. Thus, these findings suggest the intriguing possibility of modulating inter-molecular plasmon hybridization interactions in heterodimers by charge doping approaches, thereby offering new pathways for designing tunable molecular plasmonic nanostructures.\u003c/p\u003e \u003cp\u003eWe systematically characterize the absorption spectra and PI values for both peropyrene-NC under charge doping levels from \u0026minus;\u0026thinsp;2 to +\u0026thinsp;2 and for peropyrene-NO under doping from \u0026minus;\u0026thinsp;4 to +\u0026thinsp;4 (Figure S3-4 in the SM). Corresponding transition densities for bonding and antibonding states are illustrated in the insets. Comparative analysis reveals that in both positive and negative doping conditions, the maximum PI values occur under specific doping conditions (detailed data in Table S6-7 in the SM). To this end, we select the most representative cases for detailed examination: peropyrene-NC and peropyrene-NO under \u0026plusmn;\u0026thinsp;2 charge doping. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ea-d present their absorption spectra and PI values, with insets illustrating the transition densities. Furthermore, Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ee depicts the ground-state atomic charge distribution within these heterodimers. The green values quantify the net atomic charge accumulated on peropyrene-N, revealing asymmetric redistribution due to structural non-equivalence and the distinct electronegativities of nitrogen and oxygen atoms dopants. Notably, this intrinsic asymmetry fundamentally governs their excitation behavior, as evidenced by the altered optical responses.\u003c/p\u003e \u003cp\u003eBased on the analogous resonance peaks of peropyrene and peropyrene-N, coupled with their comparable responses to charge doping, the ground-state charge distribution within peropyrene-NC exerts a pronounced effect on its optical properties. As evident form the transition densities in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ea-b under \u0026plusmn;\u0026thinsp;2 charge doping, one molecule exhibits significantly stronger contributions than the other. This asymmetric contribution between two monomers suggests that the hybridization interaction in peropyrene-NC under \u0026plusmn;\u0026thinsp;2 charge doping is weaker compared to its neutral state. This is primarily attributed to the asymmetric charge distribution. Specifically, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ee, under \u0026minus;\u0026thinsp;2 charge doping, peropyrene-N carries a net charge of -1.0862 a.u., while peropyrene retains\u0026thinsp;\u0026minus;\u0026thinsp;0.9138 a.u. Due to their responses to charge doping, peropyrene-N undergoes a more pronounced redshift compared to peropyrene, leading to an enhanced disparity in resonance peaks and consequently weakening the hybridization interaction within the heterodimer. Moreover, the greater redshift of peropyrene-N results in its dominant contribution to the bonding state, while the antibonding state is primarily from peropyrene. Similarly, under +\u0026thinsp;2 charge doping, peropyrene-N (0.8964 a.u.) carries a smaller net charge than peropyrene (1.1036 a.u.), resulting in a more significant redshift for peropyrene. This further diminishes the hybridization interaction in the heterodimer. Notably, the molecular contributions to the bonding and antibonding states are reversed compared to the \u0026minus;\u0026thinsp;2 charge doping case.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn contrast to peropyrene-NC, peropyrene-NO exhibits distinct evolutionary trends in plasmon hybridization due to the relatively weaker influence of charge doping on peropyrene-O, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ec-d. The transition densities reveal that under both \u0026minus;\u0026thinsp;2 and 2 charge doping conditions, the inter-molecular interaction strength in peropyrene-NO is significantly enhanced compared to its neutral state. The bonding state is predominantly contributed by peropyrene-O, while the antibonding state is primarily from peropyrene-N. Notably, further comparative analysis shows that the inter-molecular hybridization interaction is stronger under 2 charge doping than under \u0026minus;\u0026thinsp;2 charge doping. This can also be attributed to the charge distribution under ground-state condition (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e5\u003c/span\u003ee). Peropyrene-N carries a net charge of -0.5951 a.u. and 1.2687 a.u. under \u0026minus;\u0026thinsp;2 and 2 charge doping, respectively. This significantly higher charge in the latter case induces a more pronounced redshift in the plasmonic resonance peak of peropyrene-N compared to the \u0026minus;\u0026thinsp;2 charge doping case. Consequently, the resonance peaks of peropyrene-N and peropyrene-O become more closely aligned under +\u0026thinsp;2 charge doping, leading to stronger hybridization effects.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003e present a systematic analysis of the bonding and antibonding states for peropyrene-NC and peropyrene-NO under charge doping conditions, including SPCA, molecular orbital diagrams, transition dipole moment contribution maps, and atom-atom charge transfer matrix heatmaps. For peropyrene-NC, SPCA (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003ea) reveals distinct orbital transition patterns under \u0026minus;\u0026thinsp;2 charge doping. The bonding state predominantly involves HOMO-2\u0026rarr;LUMO, HOMO-1\u0026rarr;LUMO and HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;4 transitions, while the antibonding state features HOMO-2\u0026rarr;LUMO, HOMO-1\u0026rarr;LUMO and HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;3 transitions. Under charge doping, electron density shifts between monomers, with the most pronounced changes in the HOMO and LUMO orbitals. This redistribution gives rise to distinct orbital transition patterns between the bonding and antibonding states, a feature not observed in the neutral state. Importantly, the bonding state is primarily associated with molecular orbitals dominated by peropyrene-N character, while the antibonding state is dominated by peropyrene-localized orbitals, consistent with transition density observations. The changes in molecular orbital electron density also influence the charge transfer characteristics of the bonding and antibonding states, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003eb-c. Strong electron redistribution occurs in the dominant orbital contributor, while weak electron redistribution is evident in the minor contributor, consistent with the charge transfer properties in the neutral state. Notably, charge transfer between the two monomers, with the magnitude of charge transfer is no longer approximately balanced but exhibits significant asymmetry. For the bonding state, the charge transfer from peropyrene-N to peropyrene is significantly greater than that from peropyrene to peropyrene-N, whereas the antibonding state exhibits the opposite charge transfer behavior. Additionally, the transition dipole moment contribution maps further confirm weaker plasmon hybridization interactions under \u0026minus;\u0026thinsp;2 charge doping compared to the neutral state.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003ed, SPCA analysis under 2 charge doping reveals that molecular orbital electron density evolution, similar to the \u0026minus;\u0026thinsp;2 charge doping case, leads to distinct transition compositions for the bonding and antibonding states. The bonding state is primarily contributed by HOMO-4\u0026rarr;LUMO, HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;1, and HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;2 transitions, while the antibonding state is dominated by HOMO-3\u0026rarr;LUMO, HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;1, and HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;2 transitions. Importantly, the bonding state transitions mainly originate from peropyren, whereas the antibonding state is dominated by peropyrene-N. The transition dipole moment contribution maps (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e6\u003c/span\u003ee-f) demonstrate that the plasmon hybridization interaction under 2 charge doping is significantly weaker than in the neutral state but comparable to that under \u0026minus;\u0026thinsp;2 charge doping. Similar to the \u0026minus;\u0026thinsp;2 charge doping condition, orbital electron density redistribution critically influences the charge transfer characteristics of the bonding and antibonding states. Pronounced electron reorganization occurs within the primary contribution monomer, while the secondary contributor exhibits only minor rearrangement. Moreover, the bonding state demonstrates pronounced charge from peropyrene-N to peropyrene, whereas the bonding state features a reversed peropyrene to peropyrene-N charge transfer pathway.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003ePeropyrene-NO exhibits orbital electron density redistribution trends qualitatively analogous to peropyrene-NC, yet with markedly attenuated sensitivity to charge doping (Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003ea and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e7\u003c/span\u003ed). SPCA analysis unequivocally indicates that under \u0026plusmn;\u0026thinsp;2 charge doping, the bonding state transitions are exclusively dominated by peropyrene-O, while the antibonding states are dominated by peropyrene-N. This orbital selectivity directly dictates the charge transfer behavior (Figrue 7b-c and 7e-f), with the bonding states manifesting intra-molecular electron reorganization predominantly within peropyrene-O and the antibonding states corresponding to pronounced electron redistribution in peropyrene-N. Crucially, the transition dipole moment contribution maps reveal that although the inter-molecular hybridization in peropyrene-NO remains weak, it shows a doping-induced enhancement compared to the neutral state, with 2 charge doping case exhibiting stronger hybridization than under \u0026minus;\u0026thinsp;2 charge doping. Moreover, this enhanced hybridization gives rise to a distinct charge transfer pattern: 2 charge doping promotes charge transfer from peropyrene-N to peropyrene-O in both bonding and antibonding states, whereas \u0026minus;\u0026thinsp;2 charge doping induces a complete reversal, with peropyrene-O to peropyrene-N transfer prevails.\u003c/p\u003e \u003cp\u003eThe spatial distribution of transition density serves as a well-recognized metric for characterizing plasmonic oscillations. To this end, we integrate the transition density along the \u003cem\u003ex\u003c/em\u003e direction for both peropyrene-NC and peropyrene-NO under \u0026plusmn;\u0026thinsp;2 charge doping conditions, focusing on their bonding and antibonding states, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003e. For peropyrene-NC (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003ea-b), the neutral state exhibits nearly equal contributions from both constituent monomers to the transition density, hallmarking a typical close dipolar plasmon hybridization. Under charge doping, however, both bonding and antibonding states display asymmetric enhancement. One monomer\u0026rsquo;s plasmonic oscillation is dramatically amplified, while the other is strongly suppressed. This leads to weakened hybridization interaction and a transition from balanced hybrid plasmonic modes (the neutral state) to a single-molecule dominated plasmonic excitation (the charge doping states). Consequently, the PI value under charge doping exceeds that of the neutral state due to enhanced single-molecule oscillations. In stark contrast, peropyrene-NO (Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e8\u003c/span\u003ec-d) shows that major contributing monomer oscillations (peropyrene-O for the bonding state and peropyrene-N for the antibonding state) are less sensitive to charge doping, while the minor contributor undergoes significant modulation, which is more pronounced under 2 charge doping than \u0026minus;\u0026thinsp;2 charge doping. This asymmetry thus explains why the PI value of peropyrene-NO increases under charge doping, with 2 charge doping exceeding\u0026thinsp;\u0026minus;\u0026thinsp;2 charge doping, yet indicates that the system remains dominated by single-molecule plasmonic excitation, with relatively weak inter-molecular hybridization retained.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e3.4 Tailoring Plasmon Hybrid States by Static Electric Field\u003c/h2\u003e \u003cp\u003eAn external static electric field also serves as a method to tune the excitation properties of plasmons. While previous studies have demonstrated the influence of external static electric fields on the excitation properties of homodimeric nanosystems,\u003csup\u003e33\u003c/sup\u003e the effects on heterodimeric plasmonic systems remain largely unexplored. Herein, we investigate the modulation of plasmon hybridization in these heterodimers under external static electric fields ranging from \u0026minus;\u0026thinsp;0.004 a.u. to 0.004 a.u., with the electric field applied along the \u003cem\u003ex\u003c/em\u003e direction. The absorption spectra and transition densities under these conditions are shown in Figure S5-6 in the SM, while the corresponding PI values are summarized in Table S8-9 in the SM. However, peropyrene-NO exhibits negligible field-induced hybridization changes, as evidenced by nearly additive single-molecule excitations in its absorption spectra and unaltered transition densities (Figure S5-6 in the SM). Thus, we focus our analysis on the more responsive peropyrene-NC.\u003c/p\u003e \u003cp\u003eWe employ external electric fields of -0.004 a.u. and 0.004 a.u. as representative cases for detailed analysis. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003ea-b, the absorption spectra, PI values and transition densities of the hybridized modes under these fields are presented. Figure\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003ec illustrates the direction of the applied electric field and ground-state atomic charge distribution of peropyrene-NC. Under the \u0026minus;\u0026thinsp;0.004a.u. field, peropyrene-N carries a net charge of 0.0924 a.u., whereas under the 0.004 a.u. field, it bears a charge of -0.2390 a.u. Since the total system charge remains zero and both peropyrene and peropyrene-N exhibit comparable charge doping responses, the plasmonic resonance peaks of both components demonstrate comparable redshifts. Consequently, the plasmon hybridization interactions within peropyrene-NC remain largely unaltered. This conclusion is further substantiated by comparing the transition densities in the presence and absence of electric fields, which show no significant variations.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003ed-f present the SPCA analysis, molecular orbital diagrams, atom-atom charge transfer matrix heatmaps and transition dipole moment contribution maps for peropyrene-NC under an external electric field of -0.004 a.u. The results show that the molecular orbital structure remains largely unperturbed under the applied\u0026thinsp;\u0026minus;\u0026thinsp;0.004 a.u. external field (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003ed), with electron density distributions resembling those under the field-free condition and exhibiting pronounced localization in individual monomers. The bonding and antibonding states are predominantly characterized by HOMO-5\u0026rarr;LUMO and HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;4 orbital transition, consistent with the field-free case, indicating two dominant orbital transition contributions. The bonding state is primarily associated with peropyrene contributions, while the antibonding state is dominated by peropyrene-N. Notably, the disparity between these two orbital transition contributions increases, suggesting a moderate reduction in heterodimer hybridization strength, as clearly shown in the transition dipole moment contribution maps of the hybridization modes (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003ee-f). This moderate influence of the \u0026minus;\u0026thinsp;0.004 a.u. external field on molecular orbitals leads to the charge transfer characteristics of the bonding and antibonding states largely resemble those under the field-free condition. However, the increased disparity in orbital transition contributions within the hybridization modes induces more pronounced electron redistribution in monomers with dominant orbital contributions, whereas secondary contributions exhibit weaker electron reorganization, compared to the field-free case.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eApplying 0.004 a.u. external electric field induces markedly different systematic responses, as detailed in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003eg-i. SPCA analysis reveals that the bonding and antibonding states are primarily contributed by HOMO-5\u0026rarr;LUMO and HOMO\u0026rarr;LUMO\u0026thinsp;+\u0026thinsp;5 orbital transitions (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003eg). Importantly, these two transitions exhibit nearly equivalent contributions, indicating enhanced hybridization interactions in peropyrene-NC compared to the field-free condition. This finding is further corroborated by the transition dipole moment contribution distributions (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e9\u003c/span\u003eh-i), where molecular contributions to bonding and antibonding states approach parity. Particularly significant is the near-zero transition dipole moment in the antibonding state, achieving an ideal dark plasmonic excitation mode. The 0.004 a.u. external field substantially modifies the electron density distributions of molecular orbitals, with the most pronounced effects in HOMO and LUMO orbitals. The electron density evolves from monomer-localized to delocalized distributions spanning both molecular units. This redistribution of orbital electron density further modulates the charge transfer of the hybridization modes. The charge transfer characteristics of bonding and antibonding states exhibit high consistency, attributed to the similar magnitudes of dominant orbital transitions and their contributions. Significantly, four distinct charge transfer processes emerge with nearly equivalent magnitudes: intra-molecular electron redistribution within peropyrene, intra-molecular electron reorganization within peropyrene-N, electron transfer from peropyrene-N to peropyrene, and electron transfer from peropyrene to peropyrene-N.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eWe perform an integrated analysis of the transition density along the \u003cem\u003ex\u003c/em\u003e direction for both bonding and antibonding states of peropyrene-NC under various external electric fields, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e10\u003c/span\u003e. Under \u0026minus;\u0026thinsp;0.004 a.u. external electric field, the plasmonic oscillation in dominant monomers (peropyrene for the bonding state and peropyrene-N for the antibonding state) is moderately enhanced, while that in their counterparts is relatively suppressed, leading to weakened plasmon hybridization interactions. By contrast, the 0.004 a.u. external electric field renders plasmonic oscillation intensities of both monomers in the hybridized modes more comparable, thereby partially enhancing the plasmon hybridization characteristics of the heterodimer. This is further confirmed by the evolution of PI values for peropyrene-NC hybridized modes with applied electric field strength. As shown in Figure S7 in the SM, when the external field increases from \u0026minus;\u0026thinsp;0.004 a.u. to 0.004 a.u., both bonding and antibonding states exhibit progressively increasing PI values, clearly indicating the continuous enhancement of the plasmonic excitation characteristics.\u003c/p\u003e \u003cp\u003eOur investigation reveals that both charge doping and external static electric fields can effectively tailor plasmon hybridization interactions in heterodimers, albeit with distinct degrees of control. The charge doping approach demonstrates a robust capability to manipulate the plasmon hybridization modes, enabling a progressive transition from the initial hybridized plasmonic state to a single-molecule dominated plasmonic excitation mode. By contrast, external electric field modulation primarily operates within the framework of plasmon hybridization, fine-tuning the interaction strength between the heterodimer components to either approach or deviate from the ideal plasmon hybridization state. It is worth that the theoretical configurations proposed in this study are well-supported by recent experimental advances in supramolecular electrons. Specifically, experimental studies have successfully constructed stable dimer structures comprising two molecules using the scanning tunneling microscope-based break junction technique.\u003csup\u003e\u003cspan additionalcitationids=\"CR63\" citationid=\"CR62\" class=\"CitationRef\"\u003e62\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e\u003c/sup\u003e Furthermore, mechanisms such as electric field-induced assembly\u003csup\u003e\u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e65\u003c/span\u003e\u003c/sup\u003e and vibration-assisted transport\u003csup\u003e\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e\u003c/sup\u003e have been directly observed. These experimental advances provide experimental feasibility for the theoretical mechanisms discussed in this work.\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eIn this study, we investigate plasmon hybridization tailoring in peropyrene heterodimers using LR-TDDFT calculations with various analytical methods. Neutral peropyrene-NC exhibits strong plasmon hybridization with bonding and antibonding modes showing similar charge transfer characteristics within molecules, while maintaining equivalent intermolecular charge transfer magnitudes. In contrast, neutral peropyrene-NO shows almost no hybridization effects, displaying only single-molecule dominated excitations with negligible inter-molecular charge transfer. Charge doping effectively modulates these hybridization effects-attenuating strong hybridization in peropyrene-NC due to differential molecular responses to doping, while inducing previously absent hybridization in peropyrene-NO with directional electron transfer that reverses between negative and positive doping. Static electric fields provide precise control of hybridization strength in peropyrene-NC: negative fields (-0.004 a.u.) weaken hybridization by enhancing primary molecular contributions while reducing secondary contributions and inter-molecular transfer, whereas positive fields (0.004 a.u.) drive the system toward ideal hybridization with the antibonding transition dipole approaching zero and perfectly symmetric charge transfer. However, static fields show limited efficacy in inducing hybridization in peropyrene-NO. Our results indicate that combining charge doping and static electric fields can modulate molecular plasmon hybridization at the molecular scale. These observations contribute to the understanding of molecular plasmons and may be relevant for future molecular plasmonic devices requiring tailored optical responses.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthors contribution\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eY. F conceived the idea and directed the project. H. L and N. G did DFT and TDDFT calculations. H. L and Y. F analyzed the data and wrote the manuscript. All the authors revised the manuscript.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis research was supported by the National Natural Science Foundation of China (Grant No. 12274054, 12074054).\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eConflicts of interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing financial interest.\u003c/p\u003e\n\n\u003cp\u003e\u003cstrong\u003eAvailability of data and material\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe data and material that support the findings of this study are available from the corresponding author upon reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eNordlander P, Oubre C, Prodan E, Li K, Stockman MI (2004) Plasmon Hybridization in Nanoparticle Dimers. 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Angew Chem Int Ed 61:45\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"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":"plasmonics","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"plas","sideBox":"Learn more about [Plasmonics](https://www.springer.com/journal/11468)","snPcode":"11468","submissionUrl":"https://submission.nature.com/new-submission/11468/3","title":"Plasmonics","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Molecular Plasmon, Plasmon Hybridization, TDDFT, Regulate States","lastPublishedDoi":"10.21203/rs.3.rs-9229438/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9229438/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePlasmon hybridization, as a basic interaction mechanism in nanophotonics research, has gained significant attention due to its clear picture in light-matter interaction properties. This hybridization can generate modulate spectral responses, and potentially enable the design of novel photonic devices. In this study, we employ peropyrene heterodimer as a model system and apply ab initio quantum mechanical calculation to systematically investigate the regulatory effects of charge doping and static electric fields on molecular plasmon hybridization behavior. Our results reveal that charge doping significantly alters plasmon hybridization modes, transforming strong hybridization states into a single molecule dominated plasmon excitations or even inducing new hybridization effects. Moreover, electric field regulation offers more precise control, allowing fine-tuning of hybridization strength while maintaining the original framework. These findings characterize the plasmon hybridization mechanisms at the molecular scale, which may be relevant for exploring tunable nanophotonic applications based on molecular plasmons.\u003c/p\u003e","manuscriptTitle":"Tailoring Plasmon Hybrid States in Peropyrene Heterodimers by Charge Doping and Static Electric Field","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-04-01 14:31:35","doi":"10.21203/rs.3.rs-9229438/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-04-09T15:04:58+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-04-08T14:20:37+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"110044436645450985106831772139951558592","date":"2026-04-06T21:21:43+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-03-30T16:19:32+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-03-27T02:41:44+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2026-03-27T02:41:33+00:00","index":"","fulltext":""},{"type":"submitted","content":"Plasmonics","date":"2026-03-26T05:18:22+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"plasmonics","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"plas","sideBox":"Learn more about [Plasmonics](https://www.springer.com/journal/11468)","snPcode":"11468","submissionUrl":"https://submission.nature.com/new-submission/11468/3","title":"Plasmonics","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"ddb051c9-3726-4833-b5f1-60bc09411457","owner":[],"postedDate":"April 1st, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-04-27T16:03:46+00:00","versionOfRecord":{"articleIdentity":"rs-9229438","link":"https://doi.org/10.1007/s11468-026-03361-9","journal":{"identity":"plasmonics","isVorOnly":false,"title":"Plasmonics"},"publishedOn":"2026-04-23 15:58:00","publishedOnDateReadable":"April 23rd, 2026"},"versionCreatedAt":"2026-04-01 14:31:35","video":"","vorDoi":"10.1007/s11468-026-03361-9","vorDoiUrl":"https://doi.org/10.1007/s11468-026-03361-9","workflowStages":[]},"version":"v1","identity":"rs-9229438","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9229438","identity":"rs-9229438","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}