The Journal of Physical Chemistry A最新文献_第2页

Ab Initio Kinetics for Hydrogen Abstraction from Aldehydes and Alcohols by CH₃Ȯ Radicals. CH3Ȯ自由基从醛和醇中提取氢的从头算动力学。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-29 Epub Date: 2025-05-16 DOI: 10.1021/acs.jpca.5c01163

Mengmeng Jia, Xuan Ren, Jiaxin Xie, Ruoyue Tang, Song Cheng, Fang Wang, Shuyuan Liu, Daming Zhou, Yang Li

{"title":"Ab Initio Kinetics for Hydrogen Abstraction from Aldehydes and Alcohols by CH3Ȯ Radicals.","authors":"Mengmeng Jia, Xuan Ren, Jiaxin Xie, Ruoyue Tang, Song Cheng, Fang Wang, Shuyuan Liu, Daming Zhou, Yang Li","doi":"10.1021/acs.jpca.5c01163","DOIUrl":"10.1021/acs.jpca.5c01163","url":null,"abstract":"The process of hydrogen abstraction by methoxy radicals (CH3Ȯ) represents a fundamental reaction class in hydrocarbon combustion chemistry, playing a pivotal role in fuel decomposition kinetics and radical chain propagation mechanisms. The reaction rate constants for hydrogen abstraction from C1-C2 aldehydes and C1-C3 alcohols by CH3Ȯ radicals are systematically studied by using high-level quantum chemical calculations. Geometry optimization, determination of vibrational frequency, and dihedral angle scans are conducted with the M06-2X/6-311++G(d,p) approach. The QCISD(T)/cc-pVXZ (X = D, T) and MP2/cc-pVXZ (X = D, T, and Q) levels of theory are employed for calculating the single-point energies. Rate constants are derived using transition-state theory, which incorporates quantum mechanical effects, while the thermochemical properties are obtained through statistical thermodynamics. Rate comparisons are conducted for abstracting hydrogen from different sites for a given molecule and from a specific site in different molecules. All computational results are subsequently integrated into the NUIGMech1.3 model to evaluate their impact on the prediction of ignition delay times (IDTs). The results indicate that the newly introduced thermodynamic and kinetic parameters have a significant effect on the IDTs of NC3H7OH and IC3H7OH. Sensitivity and flux analyses are conducted to determine the essential reactions that govern the observed phenomena.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4745-4756"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074860","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}

引用次数: 0

Astrochemical Significance of C₂H₇NO Isomers: A Computational Perspective on Their Stability and Detectability. C2H7NO异构体的天体化学意义：稳定性和可探测性的计算视角。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-29 Epub Date: 2025-05-15 DOI: 10.1021/acs.jpca.5c01086

Lisset Noriega, Luis Armando Gonzalez-Ortiz, Filiberto Ortíz-Chi, Gabriel Merino

引用次数: 0

Mechanisms of Temperature Control of Singlet Fission in an Optical Cavity. 光学腔中单线态裂变的温度控制机制。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-29 Epub Date: 2025-05-15 DOI: 10.1021/acs.jpca.5c01112

Haomin Xiao, Kewei Sun, Xiao Wang, Maxim F Gelin, Yang Zhao

{"title":"Mechanisms of Temperature Control of Singlet Fission in an Optical Cavity.","authors":"Haomin Xiao, Kewei Sun, Xiao Wang, Maxim F Gelin, Yang Zhao","doi":"10.1021/acs.jpca.5c01112","DOIUrl":"10.1021/acs.jpca.5c01112","url":null,"abstract":"We investigate the mechanisms of temperature control in conical-intersection-mediated singlet fission (SF) within optical cavities. Using the multiple Davydov D2 Ansatz combined with the thermo-field dynamics formalism, we model the quantum dynamics of a rubrene dimer coupled to an optical cavity at finite temperatures. The work explores the influence of temperature, cavity-matter coupling strength, photon frequency, and cavity loss on the triplet-triplet population dynamics. Results reveal that temperature enhances SF efficiency via thermal activation of coupling modes and assists in overcoming potential barriers between singlet and triplet states. It is found that strong photon-matter coupling and high photon frequencies also promote SF under conditions of resonance with excited vibronic states, while cavity losses and increased photon numbers can inhibit the process. Increased average photon numbers suppress SF as the polaritonic conical intersections shift away from the Franck-Condon region, although a photon-assisted SF effect is revealed for specific values of the average photon number at low temperatures. The study provides insights into the temperature control mechanisms of SF in optical cavities, offering potential directions for designing functional optical cavities to enhance SF efficiency, with implications for organic photovoltaics and other energy transfer technologies.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4786-4797"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074936","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}

引用次数: 0

TrIP2: Expanding the Transformer Interatomic Potential Demonstrates Architectural Scalability for Organic Compounds. TrIP2：扩展变压器原子间势证明有机化合物的结构可扩展性。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-29 Epub Date: 2025-05-15 DOI: 10.1021/acs.jpca.5c00391

Joshua Ebbert, Bryce Hedelius, Jyothish Joy, Daniel H Ess, Dennis Della Corte

{"title":"TrIP2: Expanding the Transformer Interatomic Potential Demonstrates Architectural Scalability for Organic Compounds.","authors":"Joshua Ebbert, Bryce Hedelius, Jyothish Joy, Daniel H Ess, Dennis Della Corte","doi":"10.1021/acs.jpca.5c00391","DOIUrl":"10.1021/acs.jpca.5c00391","url":null,"abstract":"TrIP2 is an advanced version of the transformer interatomic potential (TrIP) trained on the expanded ANI-2x data set, including more diverse molecular configurations with sulfur, fluorine, and chlorine. It leverages the equivariant SE(3)-transformer architecture, incorporating physical biases and continuous atomic representations. TrIP was introduced as a highly promising transferable interatomic potential, which we show here to generalize to new atom types with no alterations to the underlying model design. Benchmarking on COMP6 energy and force calculations, structure minimization tasks, torsion drives, and applications to molecules with unexpected conformational energy minima demonstrates TrIP2's high accuracy and transferability. Direct architectural comparisons demonstrate superior performance against ANI-2x, while holistic model evaluations─including training data and level-of-theory considerations─show comparative performance with state-of-the-art models like AIMNet2 and MACE-OFF23. Notably, TrIP2 achieves state-of-the-art force prediction performance on the COMP6 benchmarks and closely approaches DFT-optimized structures in torsion drives and geometry optimization tasks. Without requiring any architectural modifications, TrIP2 successfully capitalizes on additional training data to deliver enhanced generalizability and precision, establishing itself as a robust and scalable framework capable of accommodating future expansions or applications to new domains with minimal reengineering.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4757-4766"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074937","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}

引用次数: 0

Exploring the Effects of Fluorination at the Central Unit of Y6-Type Nonfullerene Acceptors on Photovoltaic Properties: A Computational Investigation. 探索y6型非富勒烯受体中心单元氟化对光伏性质的影响：计算研究。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-29 Epub Date: 2025-05-16 DOI: 10.1021/acs.jpca.5c02299

Zhiyun Chen, Shaohui Zheng

{"title":"Exploring the Effects of Fluorination at the Central Unit of Y6-Type Nonfullerene Acceptors on Photovoltaic Properties: A Computational Investigation.","authors":"Zhiyun Chen, Shaohui Zheng","doi":"10.1021/acs.jpca.5c02299","DOIUrl":"10.1021/acs.jpca.5c02299","url":null,"abstract":"The strategy of modification of central units of Y6-type nonfullerene acceptors (NFAs) with halogenation has become popular for designing new photovoltaic materials and has shown dramatic effects in improving photovoltaic properties. However, the underlying mechanism of how halogenation of central units of these NFAs influences photoelectric properties remains rather elusive. In this paper, focusing on two reported promising NFAs Qx-1 and Qx-2, with varying degrees of ring fusion at central units, we designed 4 new NFAs and modeled 10 NFAs systematically through fluorination at the central units. Using density functional theory (DFT) and time-dependent DFT calculations, we explore the impact of an altered fluorinated location at the central units of Qx-1 and Qx-2 on the photoelectric properties. The molecular planarity, dipole moment, electrostatic potential (ESP) and its fluctuation, exciton binding energy (Eb), singlet-triplet energy gap, and absorption spectrum are obtained with combinations of traditional hybrid or long-range corrected density functionals and Pople basis sets. We also developed a new numerical method to analyze the fluctuation of ESP quantitatively because recent reports discussed its importance. The computed data suggest that newly designed Qx2-bf and Qx2-cf are promising NFAs because they exhibit enhanced planarity, lower Eb (by at least 0.002 eV), and higher averaged ESP (by at least 0.247 kcal/mol) compared to Qx-2. We also find that fluorination of the core units reduces Eb noticeably, increases the ESP standard deviation, and raises the average ESP except for ortho (outside) substitutions. These findings offer valuable physical insights into the effects of core fluorination, which can serve as a guide for the rational design of high-performance QX-based NFAs.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4690-4701"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074933","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}

引用次数: 0

Evans-Polanyi-like Formulations for Rapidly Predicting Key Depolymerization Barriers in Xylopyranoses: Toward the Faster Development of Kinetic Models for Hemicellulose Pyrolysis. 快速预测木吡喃糖关键解聚障碍的类evans - polanyi公式：半纤维素热解动力学模型的快速发展

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-29 Epub Date: 2025-05-14 DOI: 10.1021/acs.jpca.5c00675

Leandro Ayarde-Henríquez, Jacopo Lupi, Bernardo Ballotta, Stephen Dooley

{"title":"Evans-Polanyi-like Formulations for Rapidly Predicting Key Depolymerization Barriers in Xylopyranoses: Toward the Faster Development of Kinetic Models for Hemicellulose Pyrolysis.","authors":"Leandro Ayarde-Henríquez, Jacopo Lupi, Bernardo Ballotta, Stephen Dooley","doi":"10.1021/acs.jpca.5c00675","DOIUrl":"10.1021/acs.jpca.5c00675","url":null,"abstract":"This work elucidates Evans-Polanyi-like (EPL) relations to rapidly estimate the standard activation enthalpy of three ubiquitous reaction classes playing a central role in hemicellulose pyrolysis: ring-opening, ring contraction, and elimination. These models bypass computing the reaction enthalpy by leveraging computationally cheap local and global electron-density-based chemical reactivity descriptors, such as Fukui's functions (f), electron population of C-O bonds (N), and the gross intrinsic strength bond index (Δgpair), evaluated for reactants solely. More than 270 reactions observed in twenty-eight functionalized β-d-xylopyranoses, the hemicellulose building block, are used under the 20-80% partition scheme for validating-deriving purposes. By using multilinear regression analysis, four EPL equations are proposed for informing barriers at the M06-2X/6-311++G(d,p), CBS-QB3, G4, and DLPNO-CCSD(T)-F12/cc-pVTZ-F12//M06-2X/6-311++G(d,p) levels. An adjusted coefficient of determination of 0.80 characterizes these parametric polynomials. Moreover, MAE and RMSE of ≈3.3 and ≈4.1 kcal mol-1 describe the performance of the best-fitting models at DFT and G4. Conversely, the highest values, MAE = 3.6 and RMSE = 4.7 kcal mol-1, are associated with the CBS-QB3 level. The benchmarking of the computed activation enthalpies at 298 K yields simple functions for high-level estimations from low levels of theory with R2 ranging from 0.94 to 0.98. Extrapolating the DPLNO barriers to the complete basis set limit tends to lower them by 0.63 kcal mol-1. EPL expressions are tailored to facilitate the development of chemical kinetic models for hemicellulose pyrolysis, as the reactant structure is the only input required.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4767-4785"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144074931","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}

引用次数: 0

Exploring the Electronic Properties of Cyclic Five-Membered 1,2,3-Triazolium Ions: A Quantum Chemical Study. 探索环五元1,2,3-三唑离子的电子性质：量子化学研究。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-29 Epub Date: 2025-05-17 DOI: 10.1021/acs.jpca.5c01415

Kanika Manchanda, Nabajyoti Patra, Lahu N Dayare, Prasad V Bharatam

{"title":"Exploring the Electronic Properties of Cyclic Five-Membered 1,2,3-Triazolium Ions: A Quantum Chemical Study.","authors":"Kanika Manchanda, Nabajyoti Patra, Lahu N Dayare, Prasad V Bharatam","doi":"10.1021/acs.jpca.5c01415","DOIUrl":"10.1021/acs.jpca.5c01415","url":null,"abstract":"Cyclic nitrenium ions (CNIs) are generally stable and have found applications in chemistry, including biochemistry. Cyclic five-membered 1,2,3-triazolium ions (CFTIs) are a special class of CNIs; such moieties are found in a few medicinally important species. Though they are isoelectronic to N-heterocyclic carbenes (NHCs), they exhibit electrophilic properties (unlike nucleophilic NHCs). A few quantum chemical studies were reported, but extensive study on CFTIs is required to understand their electronic features and design species with tailored electronic properties. In this work, a thorough quantum chemical analysis has been carried out on the standard CFTI (1,3-dimethyl-1,2,3-triazolium ion). Hydride ion affinity and fluoride ion affinity parameters were estimated to evaluate the Lewis acidic character of the CFTIs. Also, the electrophilicity of these species has been estimated in terms of global electrophilicity index (ω) values. The complexation energies of CFTIs with PMe3 (ΔHPMe3) and 1,3-dimethylimidazol-2-ylidene (ΔHNHC) have also been estimated. The modulation of the electronic properties of CFTIs as a function of substitution and ring fusion has been evaluated. The correlation between ΔHPMe3 and ΔHNHC is very high (R = 0.99); this correlation helps in identifying CFTIs that may exhibit high Lewis acidic character.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4654-4666"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144085573","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}

引用次数: 0

Photoelectron Spectroscopy of Fulvenallenyl and Fluorine-Substituted Fulvenallenyl Anions. 黄醛烯基和氟取代黄醛烯基阴离子的光电子能谱。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-29 Epub Date: 2025-05-19 DOI: 10.1021/acs.jpca.5c02839

Conor J McGee, Kristen Rose McGinnis, Caroline Chick Jarrold

{"title":"Photoelectron Spectroscopy of Fulvenallenyl and Fluorine-Substituted Fulvenallenyl Anions.","authors":"Conor J McGee, Kristen Rose McGinnis, Caroline Chick Jarrold","doi":"10.1021/acs.jpca.5c02839","DOIUrl":"10.1021/acs.jpca.5c02839","url":null,"abstract":"The anion photoelectron spectra of C7H5-, C7H4F- and C7H3F2- generated in a photoemission anion source with the benzene, fluorobenzene, and p-difluorobenzene precursors, respectively, are presented and analyzed with supporting density functional theory calculations. Patterns in the mass spectra recorded for these three separate precursors suggest that the anions may be formed through C or C- addition to the benzene or fluorobenzene rings. The spectrum of C7H5- can be definitively assigned to the anion of the fulvenallenyl radical, which is the most stable structural isomer of both C7H5- and •C7H5. The spectra of C7H4F- and C7H3F2- are also consistent with fulvenallenyl structures. Assignment to a specific regioisomer of the fluorofulvenallenyl or difluorofulvenallenyl anion is less certain, though we eliminate the possibility of structures featuring a -C≡C-F group. The electron affinities of the radicals trend upward with fluorination, but only modestly, a result of delocalization of the SOMO of the neutral radical (HOMO of the anion) over the entire molecule. Computational results on the electronic and molecular structures of these species are explored.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4702-4714"},"PeriodicalIF":2.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144100993","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}

引用次数: 0

Kinetics and Mechanistic Insights into the Ozonolysis of Limona Ketone. 柠檬酮臭氧分解的动力学和机理研究。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-28 DOI: 10.1021/acs.jpca.5c02958

Shiyuan Meng, Xiaoxiao Lin, Xiaofeng Tang, Yu Xia, Ziji Ma, Liqin Jin, Christa Fittschen, Wei Liu, Milán Szőri, Béla Fiser, Weijun Zhang

{"title":"Kinetics and Mechanistic Insights into the Ozonolysis of Limona Ketone.","authors":"Shiyuan Meng, Xiaoxiao Lin, Xiaofeng Tang, Yu Xia, Ziji Ma, Liqin Jin, Christa Fittschen, Wei Liu, Milán Szőri, Béla Fiser, Weijun Zhang","doi":"10.1021/acs.jpca.5c02958","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02958","url":null,"abstract":"Limona ketone, as a significant intermediate in the oxidation of limonene, plays a crucial role in environmental and human health impacts. In this article, we present a study on the reaction kinetics and mechanism of ozonolysis of limona ketone. The rate constant for the reaction between limona ketone and ozone was measured under standard conditions of 298 K and atmospheric pressure by the absolute rate method and was determined to be (1.2 ± 0.1) × 10-16 cm3 molecule-1 s-1. The reaction products were probed online with a vacuum ultraviolet (VUV) photoionization time-of-flight mass spectrometer and utilized to elucidate the reaction mechanism with the aid of kinetics. The atmospheric lifetime of limona ketone was discussed with the present reaction rate constant of limona ketone with O3, combined with the literature-reported rate constants for OH and NO3 reaction. The present results show that in urban areas with elevated ozone levels, ozonolysis is the primary pathway for the degradation of limona ketone, and its low-volatility organic products could significantly contribute to the formation of secondary organic aerosols.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144172244","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}

引用次数: 0

Theoretical Unveiling Photoinduced Excited State Behaviors for BP(OH)₂DCEt₂ Fluorophore: Effects of Solvent Polarity. BP(OH)2DCEt2荧光团光致激发态行为的理论揭示：溶剂极性的影响。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-05-28 DOI: 10.1021/acs.jpca.5c02523

Zibo Shen, Chang Liu, Jinfeng Zhao, Jiahe Chen

{"title":"Theoretical Unveiling Photoinduced Excited State Behaviors for BP(OH)2DCEt2 Fluorophore: Effects of Solvent Polarity.","authors":"Zibo Shen, Chang Liu, Jinfeng Zhao, Jiahe Chen","doi":"10.1021/acs.jpca.5c02523","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02523","url":null,"abstract":"In this work, the influence of solvent polarities on the excited-state intramolecular proton transfer (ESIPT) process of BP(OH)2DCEt2 fluorophore has been systematically investigated in three solvents with distinct polarities (acetonitrile, chloroform, and cyclohexane) through DFT and TDDFT methodologies. We mainly focus on elucidating the related excited-state double proton transfer (ESDPT) mechanism in BP(OH)2DCEt2. We analyze geometric configurations, infrared (IR) vibrational spectra, and core-valence bifurcation (CVB) indexes to verify the enhancement of the dual hydrogen bonds in the excited state. Meanwhile, we detected the HOMO and LUMO orbitals to investigate the effects of charge redistribution on the ESIPT/ESDPT process. The reactional potential energy surfaces (PESs) are scanned and transition state (TS) forms are searched to testify the stepwise ESDPT mechanism for BP(OH)2DCEt2 systems in three solvents. We also propose that the increase of solvent polarity can promote the occurrence of the step-by-step ESDPT reaction processes for the BP(OH)2DCEt2 system based on the calculated S1-state potential energy barriers in the surrounding environment.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144172245","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}

引用次数: 0