Journal of Chemical Physics最新文献_第6页

On the anomalous behavior of aqueous solutions: Rigorous formal results and the unraveling of their microstructural origin. 水溶液的反常行为：严格的形式结果及其微观结构起源的揭示。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0289066

Ariel A Chialvo

{"title":"On the anomalous behavior of aqueous solutions: Rigorous formal results and the unraveling of their microstructural origin.","authors":"Ariel A Chialvo","doi":"10.1063/5.0289066","DOIUrl":"https://doi.org/10.1063/5.0289066","url":null,"abstract":"We unravel the formal, unambiguous relationships between the evolution of the solute-induced perturbation of the solvent environment and the consequent macroscopic manifestation of the anomalous (aka non-monotonous composition) behavior of the second and third derivatives of the excess Gibbs free energy of a binary mixture. We address some relevant issues regarding the anomalous behavior of aqueous solutions, including the identification of their molecular-based manifestation and the rigorous interpretation according to explicit cause-effect relations between the thermodynamic evidence and the molecular-based behavior in terms of the relevant fundamental structure-making/structure-breaking functions and their temperature/pressure derivatives. Because this novel approach involves no restrictions on the type of interactions and the nature of the species in solution, it provides a powerful tool to gain understanding of the role played by solute-solvent intermolecular interaction asymmetries either in the presence or absence of hydrogen bonding interactions. Finally, we illustrate the formalism through a detailed analysis of the anomalies of aqueous ethanol solutions and test some conjectured hypotheses underlying the anomalies that point to their plausible connection to changes in the hydrogen bonding between species.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144955850","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

Self-referenced readout of nanopore translocation signals using localized electrometry. 自参考读出纳米孔移位信号使用局部电测量。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0283978

Muhammad Sajeer P, Pranjal Sur, Ashok Keerthi, Manoj M Varma

{"title":"Self-referenced readout of nanopore translocation signals using localized electrometry.","authors":"Muhammad Sajeer P, Pranjal Sur, Ashok Keerthi, Manoj M Varma","doi":"10.1063/5.0283978","DOIUrl":"https://doi.org/10.1063/5.0283978","url":null,"abstract":"For the past two decades, the ionic current blockade-based readout approach has been the basis of nanopore single-molecule sensing technology. Here, we introduce \"nanopore electrometry,\" a readout method based on measuring the modulation of the local electric field due to the translocation of the target molecule. Through comprehensive multiphysics and molecular dynamics simulations, we establish the unique strengths of nanopore electrometry that can open up new frontiers in nanopore based molecular detection. For instance, electric field concentration inside the nanopore combined with the rapid decay of the field due to charge screening leads to an asymmetric sensitivity of nanopore electrometry to the charge of the target, i.e., one can sense only cations or only anions depending on the location of the electric field sensor or the direction of the external electric field. Furthermore, simultaneous measurements from multiple local electric field sensors can be utilized for self-referenced error correction and to compensate for translocation velocity fluctuations. Finally, nanopore electrometry can also be used to detect translocations without requiring liquid electrolytes.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144955941","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

The effect of acceptor-donor-acceptor molecule bending on the symmetry breaking charge transfer and transition dipole moment. 受体-供体-受体分子弯曲对对称破缺电荷转移和跃迁偶极矩的影响。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0286467

Anatoly I Ivanov

{"title":"The effect of acceptor-donor-acceptor molecule bending on the symmetry breaking charge transfer and transition dipole moment.","authors":"Anatoly I Ivanov","doi":"10.1063/5.0286467","DOIUrl":"https://doi.org/10.1063/5.0286467","url":null,"abstract":"This study investigates the influence of molecular bending on excited-state symmetry-breaking charge transfer (SBCT) and transition dipole moments (TDMs) in donor-acceptor (A-D-A/D-A-D) systems with identical acceptors (or donors). The main conclusion is that SBCT, or exciton localization, is hindered in bent molecules. The proposed model introduces a key novelty: two reaction coordinates are required to describe SBCT in bent molecules, whereas linear systems can be adequately described by using a single coordinate. The model predicts that (i) bending reduces the degree of dissymmetry and induces nonmonotonic changes in the dipole moment, and (ii) the TDM of fluorescence exhibits monotonic increase or decrease with bending, contingent on the parity of the lower excited state. Crucially, the two-dimensional framework accounts for both the magnitude changes and rotational effects of the dipole moment and the TDM. The predictions of the model are aligned with available experimental data, validating its conclusions. Additionally, the article provides simple formulas for quantifying symmetry-breaking extent and TDM magnitudes (for absorption and fluorescence), offering practical utility for experimentalists in designing studies and interpreting results. These insights advance the design of optoelectronic materials, where controlled symmetry breaking is critical.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144955986","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

Backscattering of Li+ ions from MoS2: Probing charge transfer through experiment and theory. MoS2中Li+离子的后向散射：通过实验和理论探测电荷转移。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0283586

P Buitrago, M A Romero, R Vidal, Evelina A García, F Bonetto

{"title":"Backscattering of Li+ ions from MoS2: Probing charge transfer through experiment and theory.","authors":"P Buitrago, M A Romero, R Vidal, Evelina A García, F Bonetto","doi":"10.1063/5.0283586","DOIUrl":"https://doi.org/10.1063/5.0283586","url":null,"abstract":"We present a combined experimental and theoretical study of charge exchange dynamics in low-energy Li+ collisions with a MoS2 surface, focusing on the neutralization of backscattered projectiles. Using low-energy ion scattering, we measure charge-state-resolved time-of-flight spectra for incident energies between 2.5 and 8.0 keV, under different scattering geometries and azimuthal orientations. The results reveal neutralization fractions ranging from 20% to 35% for projectiles scattered from Mo atoms, with a slight but reproducible increase with increasing energy. These values correspond exclusively to single binary collisions between Li and Mo atoms, with negligible formation of negative ions and no significant dependence on azimuthal or entrance/exit angles. The experimental results are interpreted using a time-dependent resonant charge transfer model based on the Anderson Hamiltonian in the infinite-U limit. The model incorporates the interaction of the Li 2s level with the Mo-projected local density of states, calculated within a bond-pair formalism. Theoretical predictions reproduce well the magnitude of the measured neutral fractions, although they underestimate their energy dependence at higher energies, an effect possibly related to the omission of excited-state channels such as the Li 2p level. A qualitative comparison with charge transfer involving sulfur atoms reveals consistent trends but a systematic overestimation by the model, likely due to reionization effects in complex multi-atom trajectories. These results demonstrate the importance of local electronic structure in charge exchange processes and highlight the need for extended models that include excited states and multi-site interactions.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144955353","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

Erratum: "First-principles evaluation of the second harmonic generation response of reference organic and inorganic crystals" [J. Chem. Phys. 158, 064707 (2023)]. 校正：“参考有机和无机晶体二次谐波产生响应的第一性原理评价”[J]。化学。物理学报，2016,39(5):559 - 567。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0293813

François Mairesse, Lorenzo Maschio, Benoît Champagne

引用次数: 0

Exploring the role of chaos in model recollision processes. 探索混沌在模型记忆过程中的作用。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0257893

Jonathan Berkheim, David J Tannor

引用次数: 0

Exact factorization ansatz of the ground state many-body wave function: A case study of quartic potential problem. 基态多体波函数的精确分解分析：以四次位问题为例。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0251793

Zhiyuan Yin, Yi Deng, Xinyao Wang, Chen Li

引用次数: 0

Optimizing machine learning interatomic potentials for hydroxide transport: Surprising efficiency of single-concentration training. 优化氢氧化物传输的机器学习原子间电位：单浓度训练的惊人效率。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0284063

Jonas Hänseroth, Christian Dreßler

{"title":"Optimizing machine learning interatomic potentials for hydroxide transport: Surprising efficiency of single-concentration training.","authors":"Jonas Hänseroth, Christian Dreßler","doi":"10.1063/5.0284063","DOIUrl":"https://doi.org/10.1063/5.0284063","url":null,"abstract":"We investigate the transferability of machine learning interatomic potentials across concentration variations in chemically similar systems, using aqueous potassium hydroxide solutions as a case study. Despite containing identical chemical species (K+, OH-, and H2O) across all concentrations, models fine-tuned on specific KOH concentrations exhibit surprisingly poor transferability to others, with force prediction errors increasing dramatically from 30 meV Å-1 (at training concentration) to 90 meV Å-1 (at very different concentrations). This reveals a critical limitation when applying such models beyond their training domain, even within chemically homogeneous systems. We demonstrate that strategic selection of training data can substantially overcome these limitations without requiring extensive computational resources. Models fine-tuned on intermediate concentrations (6.26 mol l-1) exhibit remarkable transferability across the entire concentration spectrum (0.56-17.89 mol l-1), often outperforming more computationally expensive models trained on multiple concentration datasets. This approach enables accurate simulation of hydroxide transport dynamics across varying electrolyte conditions while maintaining near-quantum accuracy. Our simulations further reveal the emergence of hydroxide-hydroxide hydrogen bonding at high concentrations-a phenomenon not explicitly represented in dilute training data but successfully captured by our intermediate-concentration model. This work establishes practical guidelines for developing broadly applicable machine learning force fields with optimal transferability, challenging the assumption that diverse training datasets are always necessary for robust performance in similar chemical environments.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144955812","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

Single-atom catalysts based on one-dimensional metal porphyrin chains toward oxygen reduction reactions. 基于一维金属卟啉链的氧还原反应单原子催化剂。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0280114

Chen Liang, Haiyang Gao, Chuncai Kong, Zhimao Yang, Tao Yang

{"title":"Single-atom catalysts based on one-dimensional metal porphyrin chains toward oxygen reduction reactions.","authors":"Chen Liang, Haiyang Gao, Chuncai Kong, Zhimao Yang, Tao Yang","doi":"10.1063/5.0280114","DOIUrl":"https://doi.org/10.1063/5.0280114","url":null,"abstract":"Single-atom catalysts has emerged as a groundbreaking concept in catalysis, where individual metal atoms are anchored on supports such as carbon-based materials, oxides, or nitrides, serving as isolated active sites for catalytic reactions. In the present study, we theoretically explore the geometries, bonding properties, electronic structures, and potential catalytic performances of the recently synthesized one-dimensional (1D) M-porphyrin chains, in which the M-N4-C motif acts as the active site for oxygen reduction reactions (ORRs). Three configurations of 1D M-porphyrin chains (M = Ni, Zn) were investigated, including (a) M-porphyrin ribbon, (b) butadiyne-linked M-porphyrin, and (c) M-porphyrin-fused graphene nanoribbons. The calculation results reveal that all those 1D M-porphyrin chains are semiconductors. Energy decomposition analysis combined with natural orbital for chemical valence (EDA-NOCV) shows that the metal-ligand interaction in Ni-porphyrin is stronger than that in Zn-porphyrin. Compared to Zn-porphyrin chains, Ni-porphyrin chains exhibit stronger adsorption and superior electron transfer capabilities, which is attributed to enhanced orbital hybridization between the Ni 3d atomic orbitals and adsorbed oxygen 2p orbitals. The catalytic reaction pathways of these chains are similar for all those SACs and depend slightly on linker types, highlighting the importance of the local environment of the M-N4-C coordination framework. These findings provide valuable insights into the design of SACs with tailored properties, offering significant potential for applications in energy conversion and environmental catalysis.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144955935","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

The microcanonical Lindemann mechanism for unimolecular reactions. 单分子反应的微规范林德曼机制。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0280949

David M Leitner

{"title":"The microcanonical Lindemann mechanism for unimolecular reactions.","authors":"David M Leitner","doi":"10.1063/5.0280949","DOIUrl":"https://doi.org/10.1063/5.0280949","url":null,"abstract":"The microcanonical analog of the Lindemann mechanism for unimolecular reactions, or microcanonical Lindemann mechanism (MLM), is discussed. The mechanism makes explicit a central role of intramolecular vibrational redistribution (IVR) in mediating rates of unimolecular reactions. Under conditions of ergodic dynamics, the MLM predicts single-exponential kinetics with a rate constant that is generally smaller than the Rice-Ramsperger-Kassel-Marcus (RRKM) theory estimate. The RRKM theory rate is reached in the limit where rates of IVR from states of the activated complex to non-reactive states of the reactant are much greater than rates of transition from states of the activated complex to states of the product. We discuss the MLM in the context of experimental results for conformational isomerization, one irreversible, the photoisomerization of trans-stilbene, and another reversible, cyclohexane ringinversion. This Perspective aims to address and clarify misunderstandings that persist as to the role of IVR in unimolecular reaction kinetics. We also discuss, in the context of the MLM, a means to estimate rates of vibrational relaxation from states of the activated complex to non-reactive states from available energy-dependent unimolecular reaction rate data, which we believe is new.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144955989","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