The Journal of Physical Chemistry A最新文献_第4页

Simulating Ionized States in Realistic Chemical Environments with Algebraic Diagrammatic Construction Theory and Polarizable Embedding. 用代数图解构造理论和极化嵌入模拟现实化学环境中的电离态。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 Epub Date: 2025-01-16 DOI: 10.1021/acs.jpca.4c07742

James D Serna, Alexander Yu Sokolov

{"title":"Simulating Ionized States in Realistic Chemical Environments with Algebraic Diagrammatic Construction Theory and Polarizable Embedding.","authors":"James D Serna, Alexander Yu Sokolov","doi":"10.1021/acs.jpca.4c07742","DOIUrl":"10.1021/acs.jpca.4c07742","url":null,"abstract":"Theoretical simulations of electron detachment processes are vital for understanding chemical redox reactions, semiconductor and electrochemical properties, and high-energy radiation damage. However, accurate calculations of ionized electronic states are very challenging due to their open-shell nature, importance of electron correlation effects, and strong interactions with chemical environment. In this work, we present an efficient approach based on algebraic diagrammatic construction theory with polarizable embedding that allows to accurately simulate ionized electronic states in condensed-phase or biochemical environments (PE-IP-ADC). We showcase the capabilities of PE-IP-ADC by computing the vertical ionization energy (VIE) of thymine molecule solvated in bulk water. Our results show that the second- and third-order PE-IP-ADC methods combined with the basis of set of triple-ζ quality yield a solvent-induced shift in VIE of -0.92 and -0.93 eV, respectively, in an excellent agreement with experimental estimate of -0.9 eV. This work demonstrates the power of PE-IP-ADC approach for simulating charged electronic states in realistic chemical environments and motivates its further development.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1156-1167"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996337","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

OH-Detected Aromatic Microsolvation of an Organic NO Radical: Halogenation Controls the Solvation Side.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 DOI: 10.1021/acs.jpca.4c07744

Elisabeth Sennert, Giovanni Bistoni, Martin A Suhm

引用次数: 0

Accelerating Quantum Anharmonic Vibrational Calculations by Atom-Specific Hybrid Basis Set-Based Potential Energy Surface Approach. 基于原子特定混合基集的势能面方法加速量子非调和振动计算。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 Epub Date: 2025-01-19 DOI: 10.1021/acs.jpca.4c04066

Mokshi Sharma, Dhiksha Sharma, Tapta Kanchan Roy

{"title":"Accelerating Quantum Anharmonic Vibrational Calculations by Atom-Specific Hybrid Basis Set-Based Potential Energy Surface Approach.","authors":"Mokshi Sharma, Dhiksha Sharma, Tapta Kanchan Roy","doi":"10.1021/acs.jpca.4c04066","DOIUrl":"10.1021/acs.jpca.4c04066","url":null,"abstract":"The development of accurate yet fast quantum mechanical methods to calculate the anharmonic vibrational spectra of large molecules is one of the major goals of ongoing developments in this field. This study extensively explores and validates a hybrid electronic basis set approach for anharmonic vibrational calculations, where the molecule is segregated into different computational layers, and such layers are then treated with different levels of electronic basis sets. Following the system-bath model, the atoms corresponding to the active sites are treated in more accurate but computationally slower, large basis set and the rest of the atoms in less accurate but computationally faster, small basis set to construct the anharmonic hybrid potential energy surface (PES). Such a hybrid protocol for constructing an anharmonic PES is named as the atom-specific hybrid basis set (ASHBS) approach. The accuracy of the ASHBS approach is tested and established by evaluating the harmonic and anharmonic frequencies of a set of four prototype molecules. Following the ASHBS approach, for a chosen active site, the transitions of the corresponding modes are found to be closer to that of a high basis set, with a majority of target modes displaying a mean absolute error of around 3.3 cm-1, while achieving the computational acceleration of 2-3 times. This study also provides insights into determining the optimal layer size to balance computational efficiency and accuracy, offering a suitable alternative, particularly for large molecules.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"848-859"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996315","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

Insight into the Excited States in Monomers and π-Stacked Dimers of Azulene-Fused Acenes: ADC(2) and TD-DFT Studies. Azulene-Fused - acene单体和π堆叠二聚体激发态的洞察：ADC(2)和TD-DFT研究。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 Epub Date: 2025-01-21 DOI: 10.1021/acs.jpca.4c08515

Palak Mandal, Aditya N Panda

{"title":"Insight into the Excited States in Monomers and π-Stacked Dimers of Azulene-Fused Acenes: ADC(2) and TD-DFT Studies.","authors":"Palak Mandal, Aditya N Panda","doi":"10.1021/acs.jpca.4c08515","DOIUrl":"10.1021/acs.jpca.4c08515","url":null,"abstract":"Charge transfer (CT) states in polycyclic aromatic hydrocarbons play crucial roles in determining their electronic properties and their potential applications in organic electronics. In this work, we investigate the nature of the excited states in monomers and π-stacked dimers of azulene-fused naphthalene and anthracene systems, focusing on the interplay between structure and excited-state properties. Four different isomers for azulene-fused naphthalene (NapAz-A, NapAz-B, NapAz-C, and NapAz-D) and anthracene (AntAz-A, AntAz-B, AntAz-C, and AntAz-D) are considered. The excited-state studies are performed at the SCS-ADC(2) level and at the TD-DFT level using CAM-B3LYP, SCS-ωB2GP-PLYP, and SCS-RSX-QIDH functionals. For the monomers, the SCS-ADC(2) results reveal that states with CT characters are different in naphthalene- and anthracene-based systems. In π-stacked dimers, a few of the excited states are of the charge resonance (CR) type in NapAz-A, NapAz-B, and NapAz-C and the intermolecular CT type in NapAz-D. Similarly, AntAz-A, AntAz-B, and AntAz-D have some CR type excited states, whereas the AntAz-C isomer has intramolecular CT type excited states. Overall, among the three DFT functionals considered, CAM-B3LYP has been found to reproduce well the SCS-ADC(2) excited results in both monomers and π-stacked dimers.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1085-1098"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996331","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

Photodissociation Dynamics of Formic Acid at 230 nm: A Computational Study of the CO and CO₂ Forming Channels. 甲酸在230 nm光解动力学：CO和CO2形成通道的计算研究。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 Epub Date: 2025-01-16 DOI: 10.1021/acs.jpca.4c07933

Yi-Sin Ku, Po-Yu Tsai

{"title":"Photodissociation Dynamics of Formic Acid at 230 nm: A Computational Study of the CO and CO2 Forming Channels.","authors":"Yi-Sin Ku, Po-Yu Tsai","doi":"10.1021/acs.jpca.4c07933","DOIUrl":"10.1021/acs.jpca.4c07933","url":null,"abstract":"Recent photolysis experiments with formic acid suggest that the roaming mechanism is a significant CO-forming pathway at a photolysis energy of 230 nm. While previous computational studies have identified multiple dissociation pathways for CO-forming channels, the dynamic features of these pathways remain poorly understood. This study investigates the dissociation dynamics of the CO + H2O and CO2 + H2 channels in the ground state (S0) of formic acid using direct dynamics simulation and the generalized multi-center impulsive model (GMCIM) at 230 nm. Computational results summarize the characteristics of the product states from six different dissociation pathways, including two roaming pathways. A comparison of the simulated speed distribution of CO products with experimental observations shows that high-rotational CO products predominantly originate from the three-center dissociation pathway. Furthermore, while experimental results reveal a bimodal speed distribution of CO at low rotational states, our findings suggest that the OH roaming pathway contributes to the fast component of this distribution, rather than the slow component. Furthermore, another isomerization-mediated four-center pathway contributes negligibly to the experimental results. The agreement between computational results and experimental observations at 230 nm supports the previously proposed dissociation mechanism of the CO + H2O channel. For the CO2 + H2 channel, this study provides useful information for experimental identification of dissociation pathways in the future.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1068-1084"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996334","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

Reaction Path-Resolved Quantum Transition State Framework Using Hyperspherical (APH) Coordinates: The Geometric Phase Effects in the H + H₂ Reaction. 反应路径-用超球面（APH）坐标解析的量子过渡态框架：H + H2反应中的几何相位效应。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 Epub Date: 2025-01-21 DOI: 10.1021/acs.jpca.4c08460

Yajian Shu, Hailin Zhao, Zhigang Sun

{"title":"Reaction Path-Resolved Quantum Transition State Framework Using Hyperspherical (APH) Coordinates: The Geometric Phase Effects in the H + H2 Reaction.","authors":"Yajian Shu, Hailin Zhao, Zhigang Sun","doi":"10.1021/acs.jpca.4c08460","DOIUrl":"10.1021/acs.jpca.4c08460","url":null,"abstract":"The quantum transition state framework was developed to calculate the reaction path-resolved scattering matrix for atom-diatom reactions in hyperspherical (APH) coordinates. This approach allows for simply and directly calculating the reaction path-resolved scattering matrix, especially when the encircling reaction path is negligible. It could be used to determine the reactivities of specific pathways in a chemical reaction, providing insights into phenomena such as geometric phase effects. To validate our method, detailed calculations for the H + H2 reaction at J = 0, 1, 2 were carried out, and the results were compared with those from our previous theoretical models including the geometric phase effects. Analysis of the path-resolved reaction probabilities reveals that encircling paths play a very minor role in this reaction, even at energies exceeding the conical intersection minimum. Furthermore, the analysis suggests that the geometric phase effects arising from the interferences between different reactive pathways could become more significant for highly rotationally excited reactants and products.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"1180-1193"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996336","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

Understanding Anionic Hyperporphyrins: TDDFT Calculations on Peripherally Deprotonated meso-Tetrakis(4-hydroxyphenyl)porphyrin.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 DOI: 10.1021/acs.jpca.4c07216

Jeanet Conradie, Carl C Wamser, Abhik Ghosh

{"title":"Understanding Anionic Hyperporphyrins: TDDFT Calculations on Peripherally Deprotonated meso-Tetrakis(4-hydroxyphenyl)porphyrin.","authors":"Jeanet Conradie, Carl C Wamser, Abhik Ghosh","doi":"10.1021/acs.jpca.4c07216","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07216","url":null,"abstract":"Presented herein is a DFT/TDDFT study of meso-tetrakis(4-hydroxyphenyl)porphyrin (H2[THPP]) and its O-deprotonated tetraanionic form; the latter was modeled as both a free tetraanion and with various counterions. Based on our calculations, the experimentally observed hyperporphyrin spectra are attributed to an admixture of phenol/phenoxide character into the a2u-type HOMO of tetraphenylporphyrin. The admixture results in an elevation of the orbital energy of the HOMO in relation to other frontier orbitals, which accounts for the observed spectral redshifts. The calculations underscore differences in the performance of different exchange-correlation functionals. Thus, while the popular hybrid functional B3LYP greatly exaggerates the redshift of the far-red hyperporphyrin band of O-deprotonated H2[THPP], the range-separated functional CAMY-B3LYP predicts a more moderate redshift. The latter, however, fails to reproduce experimentally observed absorptions in the 550-600 nm range, potentially underscoring the still imperfect modeling of anionic hyperporphyrins.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062518","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 Mechanism of the Thermal Isomerization of Cyclopropane to Propene: A Comprehensive Theoretical Study. 环丙烷热异构化为丙烯的动力学和机理：综合理论研究。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 Epub Date: 2024-11-26 DOI: 10.1021/acs.jpca.4c05315

Yeljair Monascal, María P Badenes

{"title":"Kinetics and Mechanism of the Thermal Isomerization of Cyclopropane to Propene: A Comprehensive Theoretical Study.","authors":"Yeljair Monascal, María P Badenes","doi":"10.1021/acs.jpca.4c05315","DOIUrl":"10.1021/acs.jpca.4c05315","url":null,"abstract":"The kinetics of the homogeneous gas-phase thermal isomerization of cyclopropane to propene has been studied theoretically to clarify existing discrepancies regarding the interpretation of its mechanism. High-level ab initio and density functional theory calculations were used to determine the branching ratios of the biradical and carbene reaction channels over wide temperature and pressure ranges. For this, relevant molecular and thermochemical properties of the proposed intermediates and related transition states were computed and compared with literature values. The Arrhenius equation, derived between 400 and 1400 K in the high-pressure limit at the CCSD(T)/6-311++G(3df,3pd)//CCSD/6-311++G(d,p) level of theory, is given by log10(koverall,∞/s-1) = (15.60 ± 0.06) - (65.70 ± 0.17) kcal mol-1 (2.303 RT)-1. This expression is in very good agreement with the available experimental data. According to these results, the biradical pathway is the predominant mechanism, while the carbene pathway contributes 1-2% at higher temperatures. The G4//B3LYP/6-311++G(3df,3pd) and G4//M06-L/6-311++G(3df,3pd) levels showed comparable Arrhenius parameters. Low-pressure limit rate coefficients and falloff curves were also estimated to evaluate the effect of pressure on the reaction. Additionally, the possibility of a concerted path is considered, but calculations showed unstable wave functions, suggesting that this mechanism would not be plausible.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"894-908"},"PeriodicalIF":2.7,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142714876","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

Dinitrogen Activation: A Novel Approach with P/B Intermolecular FLP. 二氮活化：P/B分子间FLP的新方法。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-30 Epub Date: 2025-01-18 DOI: 10.1021/acs.jpca.4c05125

Swapan Sinha, Santanab Giri

引用次数: 0

Electronically Nonadiabatic Quenching of Excited States of O₂ by Collisions with O Atoms.

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2025-01-29 DOI: 10.1021/acs.jpca.4c07991

Dandan Lu, Yinan Shu, György Lendvay, Donald G Truhlar, Hua Guo

{"title":"Electronically Nonadiabatic Quenching of Excited States of O2 by Collisions with O Atoms.","authors":"Dandan Lu, Yinan Shu, György Lendvay, Donald G Truhlar, Hua Guo","doi":"10.1021/acs.jpca.4c07991","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07991","url":null,"abstract":"The kinetics of electronically inelastic quenching of O2(a1Δg) and O2(b1Σg+) by collisions with O(3P) have been investigated using mixed quantum-classical trajectories governed by adiabatic potential energy surfaces and state couplings generated from a recently developed diabatic potential energy matrix (DPEM) for the 14 lowest-energy 3A' states of O3. Using the coherent switching with decay of mixing (CSDM) method, dynamics calculations were performed both with 14 coupled electronic states and with 8 coupled electronical states, and similar results were obtained. The calculated thermal quenching rate coefficients are generally small, but they increase with temperature. The positive temperature dependence is attributed to high-energy locally avoided crossings that can only be easily accessed by high collision energies. We find that, depending on the temperature, 86-97% of the b state quenches are into the a state with the remainder into the ground electronic state of O2. The calculated rate coefficients for quenching of O2(b1Σg+) and O2(a1Δg) by O(3P), coupled with the assumption that electronically nonadiabatic probabilities for collisions on the 3A' surfaces are similar to those on 3A″ surfaces, are compared with the available experimental results.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143062490","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