The Journal of Physical Chemistry A最新文献

{"title":"Study on the Influence of External Electric Field Control and Vibrational Quantum Effect on the Charge Separation Mechanism in Fullerene-Based Systems.","authors":"Xinyue Wang, Huijie Guo, Dawei Kang, Tõnu Pullerits, Peng Song","doi":"10.1021/acs.jpca.4c04640","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c04640","url":null,"abstract":"<p><p>Based on the DCV-C₆₀ system of fullerene acceptor organic solar cell active materials, the charge transfer process of D-A type molecular materials under the action of an external electric field (<i><b>F</b></i>_ext) was explored. Within the range of electric field application, the excited state characteristics exhibit certain regular changes. Based on reducing the excitation energy, the excitation mode shows a trend of developing toward low excited states. The effect of solvent polarity on the stability and reorganization energy of the charge transfer state was investigated. The dependence of charge separation parameters on specific molecular structures within the electric field range was studied, proving that the electric field set along the electron transfer direction can indeed accelerate charge separation. The influence of vibrational modes on the charge separation process was studied, and the results showed that the vibrational quantum tunneling effect significantly promoted the charge separation. Therefore, considering the vibrational excitation effect and the perturbation of the nuclear-electron interaction is crucial for more accurate simulation of the electron-vibration coupling process in the excited state.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study on Influence of Microwave Electric Field Direction on Evaporation Based on Molecular Dynamics.","authors":"Song Wang, Kama Huang, Song Jia, Haoyu Wang, Zirui Liu","doi":"10.1021/acs.jpca.4c07554","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07554","url":null,"abstract":"<p><p>Microwave-assisted evaporation technology is widely used today, but its molecular mechanism is not fully understood. To investigate the molecular mechanism of the influence of microwave electric field direction on water evaporation, this paper designed experiments to measure the microwave energy required to evaporate each gram of water with electric field directions parallel and perpendicular to the water surface. The temperature rise curve of the water is controlled to be consistent in both cases, and the temperature distribution of the water is made uniform by stirring. We found a stable difference in the energy absorbed by the two situations, indicating that the direction of the microwave electric field has an effect on water evaporation. In this article, the evaporation behavior of water molecules under different directional electric fields was then studied by molecular dynamics. The SPCE water molecule model, which simulates pure water systems well, was selected for this calculation. Based on the GROMOS force field, the evaporation enthalpy and surface tension of water under various conditions at constant temperature were calculated and the conclusions were analyzed. The calculated results are in agreement with the experimental results, and the influence of the evaporation enthalpy of water molecules is related to the direction of the microwave electric field.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Infrared Ion Spectroscopy of Gaseous [Cu(2,2'-Bipyridine)₃]²⁺: Investigation of Jahn-Teller Elongation Versus Compression.","authors":"Musleh Uddin Munshi, Giel Berden, Jos Oomens","doi":"10.1021/acs.jpca.4c07019","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07019","url":null,"abstract":"<p><p>Symmetry breaking is ubiquitous in chemical transformations and affects various physicochemical properties of materials and molecules; Jahn-Teller (JT) distortion of hexa-coordinated transition-metal-ligand complexes falls within this paradigm. An uneven occupancy of degenerate 3d-orbitals forces the complex to adopt an axially elongated or compressed geometry, lowering the symmetry of the system and lifting the degeneracy. Coordination complexes of Cu²⁺ are known to exhibit axial elongation, while compression is far less common, although this may be due to the lack of rigorous experimental verification. Here, we present the gas-phase vibrational spectrum of the archetypal [Cu(2,2'-bipyridine)₃]²⁺ ionic complex, obtained by infrared multiple-photon dissociation (IRMPD) spectroscopy using the widely tunable IR free-electron laser FELIX. Predicted vibrational spectra at the density functional level of theory are nearly─but not entirely─identical for the two JT-distorted geometries. We compare experimental and theoretical spectra and address the question of an axially elongated or compressed geometry of the complex, or a mixture thereof, in the gaseous ion population.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Resonances in Low-Energy Electron Collisions with Salicylic Acid.","authors":"Valéria Liberti, Pedro A S Randi, Márcio H F Bettega, Alessandra Souza Barbosa","doi":"10.1021/acs.jpca.4c07822","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07822","url":null,"abstract":"<p><p>In this work, we report elastic integral, differential, and momentum-transfer cross sections for the scattering of low-energy electrons by salicylic acid. The cross sections were calculated with the Schwinger multichannel method implemented with norm-conserving pseudopotential within the static-exchange and static-exchange plus polarization (SEP) approximations for energies up to 15 eV. In the SEP approximation, four π* resonances were found at around 0.023, 1.27, 3.60, and 6.80 eV. While the first three are shape resonances, the latter has a mixed shape and core-excited shape character. We compare our results with available measurements in the literature, and we also discuss the role of the second resonance in the production of [M-H]^- and [M-H₂]^- species through dissociative electron attachment.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Density Functional Theory Study on Reconstruction and Reversible Transformation Processes of the ZZ57 Edge Structure in Carbon Materials: Effect of Na, K, and Ca.","authors":"Tong Hao, Qian Zhou, Jinyuan Jiang, Zhaocong Ren, Wei Tan, Haoyang Song, Lei He, Dongni Shi, Hongke Qin, Yajun Li, Yiting Pan, Hongbing Zhao, Fengying Wang, Xing Wu, Yangliang Xiang, Jinping Li, Kun Li, Zheyang Liu, Jiwei Ma","doi":"10.1021/acs.jpca.4c07375","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07375","url":null,"abstract":"<p><p>The edge structures of carbonaceous materials exhibit temperature-dependent behavior on the atomic scale, with variations in the relative ratios of zigzag, reconstructed 5-7 zigzag (ZZ57), and armchair edges observed at different temperatures. Nevertheless, the mechanisms underlying the interconversion of these edge structures and the influence of the surrounding metals remain unclear. This study investigates the reconstruction and reversible transformation processes of ZZ57 edge structures in carbon materials and examines the effects of different metal atoms (Na, K, and Ca) by using density functional theory. The simplified Z57 and A57 models are selected to simulate the microscopic reaction pathways at the isolated system level. Wave function analysis is conducted to determine the physical and chemical characteristics of ZZ57 edge structures and to predict the optimal adsorption positions of the metal atoms. Results indicate that the ZZ57 edge structure reconstruction and reversible transformation are exothermic reactions that proceed favorably in the forward direction. Analysis of the ten-membered ring in the transition state structure shows that the average bond order of the C-C bond is lower than that in the benzene ring system. Thermodynamic analysis shows that Na, K, and Ca atoms reduce the chemical equilibrium constant, thereby hindering the progress of the reactions. These findings not only provide specific theoretical insights into the transformation of the ZZ57 edge structure but also offer guidance for the precise design of carbon edges and the development of practical carbon materials.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Torsion-Vibration Interactions in S₀ and S₁ Phenylsilane.","authors":"Mitchell I Griggs, Jason R Gascooke, Warren D Lawrance","doi":"10.1021/acs.jpca.4c07824","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07824","url":null,"abstract":"<p><p>We report the results of a study of the interaction between torsion and the low frequency out-of-plane silyl wag vibration in the ground, S₀, and excited, S₁, electronic states of phenylsilane. These studies follow the observation of interactions between methyl torsion and the out-of-plane methyl wagging vibration in toluene, several fluoro-substituted toluenes and <i>N</i>-methylpyrrole. The interaction leads to various spectroscopic constants becoming divorced from their usual physical meaning. It also provides a mechanism for the redistribution of vibrational energy within the electronic state. Substitution of silyl for methyl changes the electronic interactions with the phenyl ring while retaining analogous nuclear motions. Thus, comparison of phenylsilane with toluene provides insight into the role of electronic interactions on torsion-vibration interactions. It is found that there is strong mixing between silyl torsion and the out-of-plane silyl wag vibration in both the S₀ and S₁ states of phenylsilane. Interestingly, the coupling constants for phenylsilane are similar in magnitude to those for toluene. This adds to the mounting evidence that when an XH₃ group is attached to a planar frame, the interaction of torsion with the XH₃ out-of-plane wagging vibration is generic and hence this type of interaction is likely to be widespread. The spectra show that the staggered conformation is the minimum in both electronic states.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051075","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photophysical Investigation of Dyes and Dye-PMMA Systems: Insights into Absorption, Emission, and Charge Transfer Mechanisms.","authors":"Christina Kolokytha, Alexandra Sinani, Theodore Manouras, Evangelos Angelakos, Panagiotis Argitis, Nektarios N Lathiotakis, Christos Riziotis, Demeter Tzeli","doi":"10.1021/acs.jpca.4c05342","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c05342","url":null,"abstract":"<p><p>The photophysical properties of five dyes, i.e., perylene, anthracene, aminoanthracene, 1,6-diphenylhexatriene, and 7-diethylamino-4-methylcoumarin, in solvent and attached to the poly(methyl methacrylate) (PMMA) polymer, were studied via DFT and TD-DFT calculations. Their absorption and emission spectra were calculated, while for the PMMA-dye systems, their absorption spectra were measured experimentally, in good agreement with the calculated ones. In the PMMA-dye systems, charge transfer from the dye to PMMA was observed, and in the case of perylene, electron transfer from its ground state was also observed. It was found that the PMMA-dye systems can interact photochemically via laser illumination, and provided that the charge transfer will be enhanced by using the appropriate laser parameters, the systems may be candidates for the design of materials for specific nanopatterning needs.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057498","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational Study of Organotin Oxide Systems for Extreme Ultraviolet Photoresist.","authors":"Jingbin Li, Zhefeng Wang, Han Wang","doi":"10.1021/acs.jpca.4c07585","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07585","url":null,"abstract":"<p><p>With the advancement of extreme ultraviolet (EUV) lithography technology, the demand for high-performance EUV photoresists has surged. Traditional photoresists struggle to meet the stringent requirements for increasingly smaller feature sizes in semiconductor manufacturing. Among emerging candidates, tin-based materials, particularly Sn₁₂-oxo photoresists, have shown promise due to their superior EUV light absorption properties. Modifying these clusters offers a potential pathway to tailoring their properties for specific lithographic applications. In this study, we investigate the relationship between the photosensitivity of experimentally synthesized Sn₁₂-oxo photoresists and their calculable parameters with quantum chemistry calculations. Key parameters such as bonding energies between metal atoms and organic ligands, molecular ionization potential, electrostatic potential, and HOMO-LUMO gap are identified as critical for predicting photosensitivity. While current research predominantly focuses on replacing counter-anions in Sn₁₂-oxo clusters, there is limited exploration of modifications through the replacement of organic ligands. We examined the effects of electron-withdrawing and electron-donating groups as ligands on the Sn₁₂-oxo cluster's ionization potential and Sn-ligand bonding energy. Our findings suggest a strategy for designing high-performance photoresists, thereby illuminating the path to discovering novel photoresist materials.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044905","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Attosecond Rescattering of Laser-Assisted Electron-Proton Collision in Coulomb Potential.","authors":"Mohammad Noh Daud","doi":"10.1021/acs.jpca.4c07219","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07219","url":null,"abstract":"<p><p>This study investigates the motion of an electron in a Coulomb potential driven by an intense linearly polarized XUV laser pulse analyzed using Gordon-Volkov wave functions. The wave function is decomposed into spherical partial waves to model the scattered electron wave packet after the recollision with a proton. This interaction triggers high harmonic generation, producing coherent X-ray pulses with frequencies that are integer multiples of the XUV field. The research presents a novel method for achieving atomic-scale resolution at nanometer and subfemtosecond levels, enabling observation of electron-proton collisions on an attosecond time scale. It emphasizes the coupling of fields that create resonances in the scattered electron through photon energy exchange with XUV and X-ray pulses, leading to the formation of a Rydberg electron with energy levels up to <i>n</i> = 27 and angular momentum components <i>l</i> = 13 and <i>m</i> = ± 1. The combination of XUV and high-frequency X-ray fields introduces new nonperturbative nonlinear phenomena characterized by differential cross sections derived using the Floquet-Lippmann-Schwinger equation in the first-order Born approximation. The analysis shows that backward-forward scattering involves XUV-electron energy exchange, with peak intensity along the laser polarization vector, while sideways scattering, dominated by X-ray-electron interaction, peaks perpendicular to the polarization. Additionally, the laser-assisted scattering process results in temporary electron capture in a dressed proton-bound state, followed by escape and ejection, with the free electron ponderomotive energy exceeding 10<i>U</i>_<i>p</i>.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051067","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT Study of Structural, Electronic, and Charge-Transfer Properties of 2-Naphthol Azo Derivatives: Geometric, Positional, and Substituent Effects.","authors":"Tahmina Haque, Monika Akter Shompa, Khurshida Khayer","doi":"10.1021/acs.jpca.4c06467","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c06467","url":null,"abstract":"<p><p>This work represents a systematic computational study of structural and optoelectronic properties of 24 phenylazo-2-naphthol derivatives using the DFT-B3LYP/6-31 + G(d,p) method. The positional isomers of azo compounds have been designed by introducing an azophenyl unit (with and without substituents) at three different (1-, 3-, and 4-) positions of 2-naphthols. This result shows that depending on the linking position of the azophenyl unit and substituents (NO₂ and maleimide), the <i>cis</i>-azo, <i>trans</i>-azo, and hydrazo forms of our substituted azo derivatives possess distinguished UV-vis absorption and charge-transfer properties compared to unsubstituted Sudan I derivatives. Our MO calculations show that all Sudan-MI azo derivatives exhibit unique intramolecular charge transfer from the 2-naphthol-azo group as a donor to the maleimide (MI) group as an acceptor. Interestingly, whereas the <i>trans</i>-azo and hydrazo forms of Sudan-MI derivatives show ππ*CT and nπ*CT beside the ππ* and nπ* transitions, the <i>cis</i>-azo Sudan-MI derivatives exhibit mixed (nπ* + ππ*)CT along with ππ*CT, ππ*, and mixed (nπ* + ππ*) transitions. The nature and order of the main azo ππ* (S₀ → S₂) and nπ* (S₀ → S₁) transitions alter in Sudan-MI derivatives. The respective substitution of NO₂ and MI groups in Para Red and Sudan-MI series leads to the bathochromic shift of λ_max (due to π → π* transitions) in comparison to unsubstituted Sudan I derivatives, for example, the 4-positional Para Red <i>trans</i>-azo isomer (λ_max 516.9 nm) is 93.8 nm and the 4-positional Sudan-MI <i>trans</i>-azo isomer (λ_max 447.3 nm) is 24.2 nm red-shifted compared to the 4-positional Sudan I <i>trans</i>-azo isomer (λ_max 423.1 nm). The <i>cis</i>-azo forms of all positional isomers having twisted geometries show different UV-vis spectral behaviors. In general, our studies demonstrate how the variation in the structure of azo compounds impacts their optoelectronic properties, which could be useful in electronic devices.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143051070","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}