Journal of Chemical Physics最新文献_第5页

Bingel-Hirsch reaction on actinidofullerene U@C2v(9)-C82: Improved regioselectivity compared to lanthanide counterpart. 锕系富勒烯U@C2v(9)-C82的Bingel-Hirsch反应：与镧系化合物相比，提高了区域选择性。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-28 DOI: 10.1063/5.0288266

Daniel Torrens, Bei Li, Qin Wang, Laura Abella, Yang-Rong Yao, Josep M Poblet, Ning Chen, Antonio Rodríguez-Fortea

{"title":"Bingel-Hirsch reaction on actinidofullerene U@C2v(9)-C82: Improved regioselectivity compared to lanthanide counterpart.","authors":"Daniel Torrens, Bei Li, Qin Wang, Laura Abella, Yang-Rong Yao, Josep M Poblet, Ning Chen, Antonio Rodríguez-Fortea","doi":"10.1063/5.0288266","DOIUrl":"https://doi.org/10.1063/5.0288266","url":null,"abstract":"Actinidofullerenes constitute a family of fullerenes that exhibit different metal-cage interactions, electronic structures, and properties compared to lanthanidofullerenes. In this study, we investigate the reactivity of mono-uranofullerene U@C2v(9)-C82 under the Bingel-Hirsch reaction and observe significantly higher regioselectivity, along with other differences in the reaction products, compared to La@C2v(9)-C82. Two products are obtained: a cycloadduct, which is the most abundant and has been characterized by x-ray crystallography, and a minor regioisomer that is most likely a single-bond product. Density functional theory calculations can explain the experimental structure and the formation of the two products and indicate that uranium is formally U(III) in both of them. The most abundant cycloadduct is formed under kinetic control, as found for other Bingel-Hirsch adducts, whereas the single-bond product is formed after oxidation of the anionic intermediate of the conventional Bingel-Hirsch reaction. This work is a new example of the unique reactivity and chemical properties of actinidofullerenes, which arise from their distinctive actinide-fullerene interactions.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 12","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145149184","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

A Davydov Ansatz approach to accurate system-bath dynamics in the presence of multiple baths with distinct temperatures. Davydov Ansatz方法在多个不同温度的浴池中精确的系统浴池动力学。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-28 DOI: 10.1063/5.0287778

Chenlin Ma, Fulu Zheng, Kewei Sun, Lu Wang, Yang Zhao

{"title":"A Davydov Ansatz approach to accurate system-bath dynamics in the presence of multiple baths with distinct temperatures.","authors":"Chenlin Ma, Fulu Zheng, Kewei Sun, Lu Wang, Yang Zhao","doi":"10.1063/5.0287778","DOIUrl":"https://doi.org/10.1063/5.0287778","url":null,"abstract":"We perform benchmark simulations using the time-dependent variational approach with the multiple Davydov Ansatz (mDA) to study real-time nonequilibrium dynamics in a single qubit model coupled to two thermal baths with distinct temperatures. A broad region of the parameter space has been investigated, accompanied by a detailed analysis of the convergence behavior of the mDA method. In addition, we have compared our mD2 results to those from two widely adopted, numerically \"exact\" techniques: the methods of hierarchical equations of motion (HEOM) and the quasi-adiabatic path integral (QUAPI). It is found that the mDA approach in combination with thermal field dynamics yields numerically accurate, convergent results in nearly all regions of the parameter space examined, including those that pose serious challenges for QUAPI and HEOM. Our results reveal that mDA offers a highly adaptable framework capable of capturing long-time dynamics, even in challenging regimes where other methods face limitations. These findings underscore the potential of mDA as a versatile tool for exploring quantum thermodynamics, energy transfer processes, and non-equilibrium quantum systems.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 12","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145185680","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

Small matrix path integral in imaginary time. 虚时间中的小矩阵路径积分。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-28 DOI: 10.1063/5.0285317

Rapti Pal, Nancy Makri

{"title":"Small matrix path integral in imaginary time.","authors":"Rapti Pal, Nancy Makri","doi":"10.1063/5.0285317","DOIUrl":"https://doi.org/10.1063/5.0285317","url":null,"abstract":"Thermal equilibrium properties are usually obtained from the imaginary-time path integral representation of the Boltzmann operator in combination with Monte Carlo integration methods. In some situations (identical fermions or frustrated Hamiltonians), the Boltzmann matrix leads to terms of alternating sign, which leads to a sign problem that severely impacts convergence. In this paper, we develop a robust and efficient quadrature-based method suitable for computing the Boltzmann matrix for discrete systems coupled to common or local harmonic baths. By expressing the discretized path integral with the influence functional in terms of a sum of matrix products, we develop a small matrix path integral (SMatPI) decomposition that allows iterative propagation in imaginary time while circumventing the storage of tensors employed in earlier work. The method is illustrated with several examples that involve two- and three-level systems coupled to common or local baths. We show that cyclic tight-binding Hamiltonians with positive coupling parameters give rise to Boltzmann matrix elements with alternating signs, presenting a severe sign problem to Monte Carlo approaches, while the SMatPI algorithm is stable and efficient.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 12","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145191634","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

Structure-transport relations for Li+ ions at the electrolyte/polymer interface from classical molecular dynamics. 电解质/聚合物界面上Li+离子的结构-输运关系。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-28 DOI: 10.1063/5.0286381

Anh Phuong Nguyen, Gabriel D Barbosa, Ian McRobbie, Alberto Striolo

{"title":"Structure-transport relations for Li+ ions at the electrolyte/polymer interface from classical molecular dynamics.","authors":"Anh Phuong Nguyen, Gabriel D Barbosa, Ian McRobbie, Alberto Striolo","doi":"10.1063/5.0286381","DOIUrl":"https://doi.org/10.1063/5.0286381","url":null,"abstract":"Lithium-ion batteries have become indispensable in modern life due to their ability to provide efficient and reliable energy. While extensive research has been conducted on electrolyte behavior at electrode interfaces, the electrolyte/separator interface and the transport properties through it remain relatively unexplored. Yet, optimizing the transport mechanism could improve power density and reduce overheating. Lithium ions diffuse through the pore space in the separator, where an extensive interfacial surface area is in contact with the electrolyte. Experimental studies suggest that separator-electrolyte interactions may impact the surface chemistry and microscopic behavior of transport processes, but atomic-level insights are still lacking. This study uses classical molecular dynamics simulations to investigate the behavior of 1.2M LiPF6 in ethylene carbonate at the interface with a polyethylene substrate, a commonly used separator material. Our simulations reveal how the solvation structure and diffusive mechanisms change within thin interfacial films as a function of the distance from the polyethylene substrate. The results could provide a benchmark for engineering future electrolytes and separator materials to eventually control transport properties.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 12","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145191643","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

A research database for experimental electrocatalysis: Advancing data sharing and reusability. 实验电催化研究数据库：推进数据共享和可重用性。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-28 DOI: 10.1063/5.0280821

Ruchika Mahajan, Ashton M Aleman, Colin F Crago, Suman Bhasker-Ranganath, Melissa E Kreider, Jose A Zamora Zeledon, Johanna Schröder, Gaurav A Kamat, McKenzie A Hubert, Adam C Nielander, Thomas F Jaramillo, Michaela Burke Stevens, Johannes Voss, Kirsten T Winther

{"title":"A research database for experimental electrocatalysis: Advancing data sharing and reusability.","authors":"Ruchika Mahajan, Ashton M Aleman, Colin F Crago, Suman Bhasker-Ranganath, Melissa E Kreider, Jose A Zamora Zeledon, Johanna Schröder, Gaurav A Kamat, McKenzie A Hubert, Adam C Nielander, Thomas F Jaramillo, Michaela Burke Stevens, Johannes Voss, Kirsten T Winther","doi":"10.1063/5.0280821","DOIUrl":"https://doi.org/10.1063/5.0280821","url":null,"abstract":"The availability of high-fidelity catalysis data is essential for training machine learning models to advance catalyst discovery. Furthermore, the sharing of data is crucial to ensure the comparability of scientific results. In electrocatalysis, where complex experimental conditions and measurement uncertainties pose unique challenges, structured data collection and sharing are critical to improving reproducibility and enabling robust model development. Addressing these challenges requires standardized approaches to data collection, metadata inclusion, and accessibility. To support this effort, we have developed an extensive data infrastructure that curates and organizes multimodal data from electrocatalysis experiments, making them openly available through the catalysis-hub.org platform. Our datasets, comprising 241 experimental entries, provide detailed information on reaction conditions, material properties, and performance metrics, ensuring transparency and interoperability. By structuring electrocatalysis data in web-based as well as machine-readable formats, we aim to bridge the gap between experimental and computational research, allowing for improved benchmarking and predictive modeling. This work highlights the importance of well-structured, accessible data in overcoming reproducibility challenges and advancing machine learning applications in catalysis. The framework we present lays the foundation for future data-driven research in electrocatalysis and offers a scalable model for other experimental disciplines.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 12","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145191595","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

Machine learning accelerates Raman computations from molecular dynamics for materials science. 机器学习加速了材料科学分子动力学的拉曼计算。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-28 DOI: 10.1063/5.0287358

David A Egger, Manuel Grumet, Tomáš Bučko

{"title":"Machine learning accelerates Raman computations from molecular dynamics for materials science.","authors":"David A Egger, Manuel Grumet, Tomáš Bučko","doi":"10.1063/5.0287358","DOIUrl":"https://doi.org/10.1063/5.0287358","url":null,"abstract":"Raman spectroscopy is a powerful experimental technique for characterizing molecules and materials that is used in many laboratories. First-principles theoretical calculations of Raman spectra are important because they elucidate the microscopic effects underlying Raman activity in these systems. These calculations are often performed using the canonical harmonic approximation, which cannot capture certain thermal changes in the Raman response. Anharmonic vibrational effects were recently found to play crucial roles in several materials, which motivates theoretical treatments of the Raman effect beyond harmonic phonons. While Raman spectroscopy from molecular dynamics (MD-Raman) is a well-established approach that includes anharmonic vibrations and further relevant thermal effects, MD-Raman computations were long considered to be computationally too expensive for practical materials computations. In this perspective article, we highlight that recent advances in the context of machine learning have now dramatically accelerated the involved computational tasks without sacrificing accuracy or predictive power. These recent developments highlight the increasing importance of MD-Raman and related methods as versatile tools for theoretical prediction and characterization of molecules and materials.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 12","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145191657","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

Haven ratio for correlated ion hopping in oxide glasses from NMR spin-lattice relaxation. 从核磁共振自旋-晶格弛豫研究氧化玻璃中相关离子跳跃的避风港比。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-21 DOI: 10.1063/5.0289851

Sabyasachi Sen

{"title":"Haven ratio for correlated ion hopping in oxide glasses from NMR spin-lattice relaxation.","authors":"Sabyasachi Sen","doi":"10.1063/5.0289851","DOIUrl":"https://doi.org/10.1063/5.0289851","url":null,"abstract":"The ionic transport in glasses and supercooled liquids exhibits complex dynamical behavior characterized by non-exponential correlation functions, often described by stretched exponential decay. This study investigates the connection between the Haven ratio HR, which measures the deviation of diffusivity of modifier alkali cations from random walk due to their backward-correlated hopping, and the stretching exponent β of the orientational correlation function associated with the nuclear magnetic resonance spin-lattice relaxation (NMR SLR) of these alkali nuclides. By analyzing the temperature-dependent NMR SLR rate data of alkali ions in a wide range of supercooled oxide network liquids, this study reveals a hitherto unknown approximate equality between HR and β. This relationship is shown to be consistent with a model of backward-correlated hopping of mobile modifier ions in a temporally frozen oxide network. Estimation of NMR SLR β for individual alkali ions in mixed-alkali systems offers a pathway to estimate species-specific HR values that are otherwise experimentally inaccessible. These findings, when taken together, suggest that β can serve as a proxy for HR and offer new insight into the microscopic nature of glassy ion transport.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 11","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145085267","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

Kinetic pathways of coesite densification from metadynamics. 从元动力学看粘土致密化的动力学途径。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-21 DOI: 10.1063/5.0284323

David Vrba, Roman Martoňák

{"title":"Kinetic pathways of coesite densification from metadynamics.","authors":"David Vrba, Roman Martoňák","doi":"10.1063/5.0284323","DOIUrl":"https://doi.org/10.1063/5.0284323","url":null,"abstract":"We study compression of coesite to pressures above 35 GPa, substantially beyond the equilibrium transition pressure to octahedral phases (8 GPa to stishovite). Experiments at room temperature showed that up to 30 GPa the metastable coesite structure develops only minor displacive changes (coesite-II and coesite-III) while the Si atoms remain 4-coordinated. Beyond 30 GPa, reconstructive transformations start, following different pathways from the complex structure of coesite. In addition to amorphization, two different crystalline outcomes were observed. One is the formation of defective high-pressure octahedral phases [Hu et al., Nat. Commun. 6, 6630 (2015)], and another one is the formation of unusual and complex dense phases coesite-IV and coesite-V with Si atoms in 4-fold, 5-fold, and 6-fold coordination [Bykova et al., Nat. Commun. 9, 4789 (2018)]. Capturing these structural transformations computationally represents a challenge. Here, we show that employing metadynamics with Si-O coordination number and volume as generic collective variables in combination with a machine-learning based ACE potential [Erhard et al., Nat. Commun. 15, 1927 (2024)], one naturally observes all three mentioned pathways, resulting in the phases observed experimentally. We describe the atomistic mechanisms along the transformation pathways. While the pathway to coesite-IV is simpler, the transformation to octahedral phases involves two steps: first, a hcp sublattice of O atoms is formed where Si atoms occupy octahedral positions, but the octahedron chains do not form a regular pattern. In the second step, the Si atoms order and the chains develop a more regular arrangement. We predict that the pathway to coesite-IV is preferred at room temperature while, at 600 K, the formation of octahedral phases is more likely.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 11","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145085513","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 the shape of chemistry data-Applications with persistent homology. 理解化学数据的形态——具有持久同源性的应用。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-07 DOI: 10.1063/5.0281156

Joshua Bilsky, Aurora E Clark

引用次数: 0

Tutorial on computing nonadiabatic proton-coupled electron transfer rate constants. 计算非绝热质子耦合电子转移速率常数的教程。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-09-07 DOI: 10.1063/5.0284337

Phillips Hutchison, Kai Cui, Jiayun Zhong, Sharon Hammes-Schiffer

{"title":"Tutorial on computing nonadiabatic proton-coupled electron transfer rate constants.","authors":"Phillips Hutchison, Kai Cui, Jiayun Zhong, Sharon Hammes-Schiffer","doi":"10.1063/5.0284337","DOIUrl":"https://doi.org/10.1063/5.0284337","url":null,"abstract":"Proton-coupled electron transfer (PCET) is pervasive throughout chemistry, biology, and physics. Over the last few decades, we have developed a general theoretical formulation for PCET that includes the quantum mechanical effects of the electrons and transferring protons, including hydrogen tunneling, as well as the reorganization of the environment and the donor-acceptor fluctuations. Analytical rate constants have been derived in various well-defined regimes. This Tutorial focuses on the vibronically nonadiabatic regime, in which a golden rule rate constant expression is applicable. The goal is to provide detailed instructions on how to compute the input quantities to this rate constant expression for PCET in molecules, proteins, and electrochemical systems. The required input quantities are the inner-sphere and outer-sphere reorganization energies, the diabatic proton potential energy profiles, the electronic coupling, the reaction free energy, and the proton donor-acceptor distance distribution function. Instructions on how to determine the degree of electron-proton nonadiabaticity, which is important for determining the form of the vibronic coupling, are also provided. Detailed examples are given for thermal enzymatic PCET, homogeneous molecular electrochemical PCET, photochemical molecular PCET, and heterogeneous electrochemical PCET. A Python-based package, pyPCET, for computing nonadiabatic PCET rate constants, along with example scripts, input data, output files, and detailed documentation, is publicly available.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 9","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145000657","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