Journal of Chemical Physics最新文献_第2页

Imaging the photodissociation dynamics of vibrationless and vibrationally excited CH3S radicals. 无振动和振动激发的CH3S自由基光解动力学成像。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0283366

Pedro Recio, Alexandre Zanchet, David V Chicharro, Sonia Marggi Poullain, Luis Rubio-Lago, Gustavo A Pino, Luis Bañares

{"title":"Imaging the photodissociation dynamics of vibrationless and vibrationally excited CH3S radicals.","authors":"Pedro Recio, Alexandre Zanchet, David V Chicharro, Sonia Marggi Poullain, Luis Rubio-Lago, Gustavo A Pino, Luis Bañares","doi":"10.1063/5.0283366","DOIUrl":"10.1063/5.0283366","url":null,"abstract":"The photodissociation dynamics of CH3S radicals was studied at different excitation energies within the first absorption band. The CH3S radicals were produced with a broad vibrational energy distribution from the photodissociation of CH3SH at 210 nm, which allowed us to study the effect of the vibrational excitation on the photodissociation dynamics. The photofragments, CH3(ν), S(3PJ), and S(1D) were detected by resonance enhanced multiphoton ionization schemes in slice-imaging experiments, and the corresponding translational energy and angular distributions were obtained for each fragment. Vibrationless CH3S radicals are excited to the Ã2A1 state that predissociates via three possible dissociative states (ã4A2, B̃2A2, and 4E), leading to the formation of CH3(ν = 0), CH3(ν2) with inverted population and S(3PJ) with J = 0, 1, and 2. Instead, vibrationally excited CH3S radicals are excited in the Franck-Condon region of the B̃2A2 dissociative state, where they dissociate directly to produce fast and anisotropic S(3P0) fragments, according to the adiabatic correlation established by the new calculated potential energy curves reported in this work. The B̃2A2 state is crossed by the dissociative 4E state, and this crossing leads to the formation of slower and less anisotropic S(3P1) and S(3P2) fragments that apparently correlate with CH3 populated with one quantum in the C-H stretch (ν1), suggesting that this vibrational mode is involved in the non-adiabatic dynamics associated to the B̃2A2/4E crossing. Finally, S(1D) fragments show a Boltzmann-like kinetic energy distribution with an isotropic angular distribution, associated with slow fragments produced by statistical dissociation from the locally excited Ã2A1 state of CH3S.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731169","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

Nonadiabatic ring-polymer instanton rate theory: A generalized dividing-surface approach. 非绝热环-聚合物瞬态速率理论：一种广义划分曲面方法。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0279454

Rhiannon A Zarotiadis, Joseph E Lawrence, Jeremy O Richardson

{"title":"Nonadiabatic ring-polymer instanton rate theory: A generalized dividing-surface approach.","authors":"Rhiannon A Zarotiadis, Joseph E Lawrence, Jeremy O Richardson","doi":"10.1063/5.0279454","DOIUrl":"10.1063/5.0279454","url":null,"abstract":"Constructing an accurate approximation to nonadiabatic rate theory that is valid for arbitrary values of the electronic coupling has been a long-standing challenge in theoretical chemistry. Ring-polymer instanton theories offer a very promising approach to solve this problem, since they can be rigorously derived using semiclassical approximations and can capture nuclear quantum effects such as tunneling and zero-point energy at a cost similar to that of a classical calculation. A successful instanton rate theory already exists within the Born-Oppenheimer approximation, for which the optimal tunneling pathway is located on a single adiabatic surface. A related instanton theory has also been developed for nonadiabatic reactions using two weakly coupled diabatic surfaces within the framework of Fermi's golden rule. However, many chemical reactions do not satisfy the conditions of either limit. By employing a tunable dividing surface that measures the flux both along nuclear coordinates and between electronic states, we develop a generalized nonadiabatic instanton rate theory that bridges between these two limits. The resulting theory approximates the quantum-mechanically exact rates well for the systems studied and, in addition, offers a novel mechanistic perspective on nonadiabatic reactions.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731171","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

Hierarchically cactus-like nickel sulfide-lanthanum carbonate hydroxide composite for urea-assisted water splitting. 仙人掌状硫化镍-氢氧化碳酸盐复合材料用于尿素辅助水分解。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0279752

Mingliang Yang, Hua Jin, Jianfeng Song, Shiqian She, Jia Chen, Kun Xiong

{"title":"Hierarchically cactus-like nickel sulfide-lanthanum carbonate hydroxide composite for urea-assisted water splitting.","authors":"Mingliang Yang, Hua Jin, Jianfeng Song, Shiqian She, Jia Chen, Kun Xiong","doi":"10.1063/5.0279752","DOIUrl":"10.1063/5.0279752","url":null,"abstract":"Hydrogen production from water electrolysis is mainly affected by the high overpotential and slow reaction kinetics of the anodic oxygen evolution reaction (OER). Replacing slow oxygen evolution reaction (OER) with thermodynamically favorable urea oxidation reaction (UOR) is one of the feasible strategies for achieving energy-saving hydrogen production. In this work, a cactus-like nickel sulfide-lanthanum carbonate hydroxide (NiSx-LaCH) composite was synthesized on the surface of Ni foam by a hydrothermal method and sulfurization process for the first time. This cactus-like structure can significantly improve the specific surface area of the catalyst and the electrolyte accessibility. The coupling of NiSx and LaCH brought about the electron structure redistribution and enhanced the stability and conductivity. The generated synergistic effect of NiSx-LaCH/NF improved the adsorption of urea/water molecules and the intrinsic catalytic activity. It exhibited outstanding electrocatalytic performance for UOR and hydrogen evolution reaction, which can drive the current density of 100 mA cm-2 at low potentials of 1.36 V and -0.26 V, respectively. Assembling NiSx-LaCH/NF into urea electrolysis system can reduce the cell voltage by 0.22 V compared to water electrolysis. This indicates that using UOR instead of OER could achieve energy-saving hydrogen production and has promising prospects in treating urea-rich wastewater.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144731168","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

Interpretable machine learned predictions of adsorption energies at the metal-oxide interface. 可解释的机器学习预测吸附能在金属-氧化物界面。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0282674

Marius Juul Nielsen, Luuk H E Kempen, Julie de Neergaard Ravn, Raffaele Cheula, Mie Andersen

{"title":"Interpretable machine learned predictions of adsorption energies at the metal-oxide interface.","authors":"Marius Juul Nielsen, Luuk H E Kempen, Julie de Neergaard Ravn, Raffaele Cheula, Mie Andersen","doi":"10.1063/5.0282674","DOIUrl":"https://doi.org/10.1063/5.0282674","url":null,"abstract":"The conversion of CO2 to value-added compounds is an important part of the effort to store and reuse atmospheric CO2 emissions. Here, we focus on CO2 hydrogenation over so-called inverse catalysts: transition metal oxide clusters supported on metal surfaces. The conventional approach for computational screening of such candidate catalyst materials involves a reliance on density functional theory (DFT) to obtain accurate adsorption energies at a significant computational cost. Here, we present a machine learning (ML)-accelerated workflow for obtaining adsorption energies at the metal-oxide interface. We enumerate possible binding sites at the clusters and use DFT to sample a subset of these with diverse local adsorbate environments. The dataset is used to explore interpretable and black-box ML models with the aim of revealing the electronic and structural factors controlling adsorption at metal-oxide interfaces. Furthermore, the explored ML models can be used for low-cost prediction of adsorption energies on structures outside of the original training dataset. The workflow presented here, along with the insights into trends in adsorption energies at metal-oxide interfaces, will be useful for identifying active sites, predicting parameters required for microkinetic modeling of reactions on complex catalyst materials, and accelerating data-driven catalyst design.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144742215","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

Thermal equilibrium in coupled trajectory mixed quantum-classical dynamics. 耦合轨迹混合量子经典动力学中的热平衡。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-28 DOI: 10.1063/5.0274363

Aaron Dines, Jochen Blumberger

{"title":"Thermal equilibrium in coupled trajectory mixed quantum-classical dynamics.","authors":"Aaron Dines, Jochen Blumberger","doi":"10.1063/5.0274363","DOIUrl":"https://doi.org/10.1063/5.0274363","url":null,"abstract":"Detailed balance, the correct thermalization of electronic state populations, is an essential and elusive property of quantum-classical non-adiabatic dynamics methods. While some methods can reproduce detailed balance through physically well-motivated algorithmic adaptations, or by construction of a conserved Hamiltonian function, the physical mechanism leading to detailed balance is not understood from first principles. Coupled trajectory mixed quantum-classical (CTMQC) dynamics may provide some insight into the question, as it can be derived from first principles in the exact factorization theorem of full quantum mechanics. Although we find that the current conventional flavor of CTMQC, which conserves energy across the ensemble of trajectories (known as CTMQC-E), fails to reproduce detailed balance as in Ehrenfest dynamics, we show that a similar variant, where total energy is conserved on each trajectory independently, provides a major improvement over Ehrenfest with respect to detailed balance. Moreover, we show that the theory achieves convergence of the mean electronic potential energy with the number of energy levels that successively increase in energy. This new variant is shown to, by simulations on the Tully models and double arch model, retain a good description electronic populations and coherence compared to exact quantum dynamics. We explain the thermalization mechanism through the additional terms that distinguish CTMQC from Ehrenfest dynamics. We show that the improvement can be explained via geometric contributions to the nuclear force, resulting from the quantum momentum, which act to oppose motion when electrons decohere upward in energy and act to enhance motion otherwise, somewhat emulating the mechanism of frustrated hops. These results have considerable implications for the applicability of CTMQC to condensed phase simulations.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 4","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144742217","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

Large scale simulations of a detailed molecular model of seawater: Ionic conductivity and diffusion coefficients of CO2. 详细的海水分子模型的大规模模拟：离子电导率和CO2的扩散系数。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-21 DOI: 10.1063/5.0272445

Miguel A Gonzalez, David Carrasco-Busturia, Carlos Vega, Jose L F Abascal

{"title":"Large scale simulations of a detailed molecular model of seawater: Ionic conductivity and diffusion coefficients of CO2.","authors":"Miguel A Gonzalez, David Carrasco-Busturia, Carlos Vega, Jose L F Abascal","doi":"10.1063/5.0272445","DOIUrl":"https://doi.org/10.1063/5.0272445","url":null,"abstract":"Oceans are essentially an electrolyte solution. The experimental study of physical and chemical processes occurring in oceans remains challenging, so molecular dynamics simulations may be of great help. We have recently demonstrated that simulations using a state-of-the-art force field can accurately describe the thermophysical properties of seawater by employing a detailed chemical model of the solution. Here, we extend our previous work by investigating additional properties that require simulations on larger samples and time length scales. First, the extended time and size scales of our simulations allow for a relatively precise determination of the electrical conductivity, a fundamental property of seawater for which accurate experimental data are available, serving as a further test of the employed force field. Second, the incorporation of CO2 into the sample enables us to evaluate its diffusion coefficient DCO2. No experimental measurements or computational simulations have yet provided estimates of carbon dioxide diffusivity at salinity levels and compositions representative of actual oceanic environments. To validate our results, we have also determined DCO2 in pure water. Our simulation results show excellent agreement with experimental data in pure water, which reinforces our confidence in the predicted CO2 diffusivity in seawater. This study provides a rigorous test of the reliability of the Madrid-2019 force field (together with TraPPE for CO2) in saline environments. From this perspective, relevant challenges can be addressed, such as the sink of atmospheric carbon dioxide into the deeper ocean, CO2 sequestration in deep saline aquifers, and seawater freezing (for desalination purposes).","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144674846","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

Embedded random phase approximation for magnetic systems: H2 dissociative adsorption on Fe(110). 磁性系统的嵌入随机相近似：H2在Fe上的解离吸附（110）。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-21 DOI: 10.1063/5.0271416

Ziyang Wei, Emily A Carter

{"title":"Embedded random phase approximation for magnetic systems: H2 dissociative adsorption on Fe(110).","authors":"Ziyang Wei, Emily A Carter","doi":"10.1063/5.0271416","DOIUrl":"https://doi.org/10.1063/5.0271416","url":null,"abstract":"The random phase approximation (RPA), a method for treating electron correlation, has been shown to be superior to standard density functional theory (DFT) approximations in numerous cases. However, the RPA's computational cost is substantially higher than that of DFT, particularly restricting its application to extended surfaces. The recently introduced embedded RPA (emb-RPA) approach [Wei et al., J. Chem. Phys. 159(19), 194108 (2023)] reduces this computational cost by approximately two orders of magnitude. While previous applications of emb-RPA focused on non-spin-polarized systems, here we extend the approach to ferromagnetic ones. Unlike other embedded correlated wavefunction methods, such as embedded complete active space self-consistent field theory, emb-RPA is advantageous for spin-polarized systems because the RPA is compatible with unrestricted DFT solutions, which are eigenfunctions of the spin angular momentum operator Sz but not the total spin-squared operator S2. By applying emb-RPA with specific magnetization constraints, we achieved a speedup of two to three orders of magnitude (one order when accounting for the one-time embedding potential optimization cost) with only small errors (∼50 meV) compared to full periodic RPA. Moreover, emb-RPA significantly reduces the over-binding errors of DFT approximations. We anticipate that the acceleration enabled by the spin-polarized emb-RPA approach will broaden the applicability of RPA to magnetic materials.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144674844","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

Challenges in the study of chemistry and photochemistry at air-water interfaces: Toward in situ monitoring of reaction kinetics with spectroscopic techniques. 空气-水界面化学和光化学研究的挑战：利用光谱技术对反应动力学进行现场监测。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-21 DOI: 10.1063/5.0269541

Alexandra M Deal

引用次数: 0

Assembly of tubes in the stretching-dominated limit. 在拉伸控制极限下的管子组装。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-21 DOI: 10.1063/5.0271521

Carlos I Mendoza, David Reguera

{"title":"Assembly of tubes in the stretching-dominated limit.","authors":"Carlos I Mendoza, David Reguera","doi":"10.1063/5.0271521","DOIUrl":"https://doi.org/10.1063/5.0271521","url":null,"abstract":"Many biological and nanotechnological processes rely on the self-assembly of tubular structures. For this reason, theoretical models that offer insights into this process and ways to control its final outcome are essential. In this work, we study the conditions under which tubules are self-assembled spontaneously from free subunits in solution and explore the possible formation pathways using classical nucleation theory and an elastic model in the stretching-dominated regime. We find that a dimensionless number, B, that measures the relative importance of bending with respect to line tension, controls the fate and polymorphism of the tubules. In our model, the assembly process starts from the spontaneous formation of a curved patch that eventually closes into a tube following a combination of two generic mechanisms: (i) curvature fluctuations, which are dominant for B≤1 and (ii) aspect-ratio fluctuations, mainly occurring when B≫1. Using mesoscopic non-equilibrium thermodynamics, we describe the kinetics of formation of closed tubes and determine the final radii distribution of the assembled tubes, which can significantly differ from the equilibrium one. This work opens the way to optimize the efficiency of assembly and control the radius of different tubular nanostructures, such as viral, carboxysome, or DNA origami tubules.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144674839","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

Drachmanization revisited. Drachmanization再现。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-07-21 DOI: 10.1063/5.0273068

Jerzy Cioslowski

引用次数: 0