Journal of Chemical Physics最新文献_第5页

Nuclear quantum and H/D isotope effects on hydrogen-bond symmetrization in lithium hydroxide crystals at high pressure. 核量子和H/D同位素对高压氢氧化锂晶体氢键对称的影响。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0276067

Hikaru Tanaka, Kazuaki Kuwahata, Masanori Tachikawa, Taro Udagawa

{"title":"Nuclear quantum and H/D isotope effects on hydrogen-bond symmetrization in lithium hydroxide crystals at high pressure.","authors":"Hikaru Tanaka, Kazuaki Kuwahata, Masanori Tachikawa, Taro Udagawa","doi":"10.1063/5.0276067","DOIUrl":"https://doi.org/10.1063/5.0276067","url":null,"abstract":"Molecular crystals with hydrogen bonds undergo a phase transition and symmetrization of the hydrogen-bond network at high pressures. Lithium hydroxide (LiOH) also undergoes a similar phenomenon; however, the pressure at which it occurs remains unclear. This study employed the path integral molecular dynamics (PIMD) and static density functional theory calculations to investigate hydrogen-bond symmetrization in LiOH crystals at high pressures. The nuclear quantum effects centralized the protons and significantly lowered the pressure required for hydrogen-bond symmetrization (∼500 GPa in PIMD, compared with the 1200 GPa recorded in the static density functional theory calculations). Furthermore, the pressure required for symmetrization in the deuterated system [PIMD(D)] was higher than that required in the nondeuterated system [PIMD(H)]. This indicated that the H/D isotope effect significantly affects the hydrogen-bond symmetrization. These results demonstrate that nuclear quantum and isotope effects significantly affect hydrogen-bond symmetrization in LiOH under extreme conditions.","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":"144955844","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

Rotationally inelastic scattering of cyanocyclopentadiene by helium atoms. 氦原子对氰环戊二烯的旋转非弹性散射。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0282853

Karina Sogomonyan, Malek Ben Khalifa, Phoebe Pierré, Jérôme Loreau

{"title":"Rotationally inelastic scattering of cyanocyclopentadiene by helium atoms.","authors":"Karina Sogomonyan, Malek Ben Khalifa, Phoebe Pierré, Jérôme Loreau","doi":"10.1063/5.0282853","DOIUrl":"https://doi.org/10.1063/5.0282853","url":null,"abstract":"In the interstellar medium (ISM), polycylic aromatic hydrocarbons (PAHs) are believed to be an important carbon reservoir, accounting for up to a quarter of all interstellar carbon in our galaxy. This makes the investigation of their potential formation precursors highly relevant in the context of ISM chemistry. This, in turn, includes knowing the abundance of the precursor species. One of the possible precursor molecules for PAHs is the recently detected cyanocyclopentadiene, c-C5H5CN. Given the physical conditions of the dense dark molecular cloud TMC-1 where the cyclic species was detected, it is crucial to consider that local thermodynamic equilibrium conditions may not be satisfied. In such case, an accurate estimation of the molecular abundance involves taking into account the competition between the radiative and collisional processes, which requires the knowledge of rotational excitation data for collisions with the most abundant interstellar species-He or H2. In this paper, the first potential energy surface (PES) for the interaction of the most stable isomer of cyanocyclopentadiene (1-cyano-1,3-cyclopentadiene) with He atoms is computed using the explicitly correlated coupled-cluster theory [CCSD(T)-F12]. The obtained PES demonstrates high anisotropy and is characterized by a global potential well of -101.8 cm-1. Scattering calculations of the rotational (de-)excitation of 1-cyano-cyclopentadiene induced by He atoms are performed with the quantum mechanical close-coupling method for total energies up to 125 cm-1. The resulting rotational state-to-state cross sections are used to compute the corresponding rate coefficients for temperatures up to 20 K and propensity rules are also discussed.","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":"144955893","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

Study of concentration dependent microstructures and dynamic behaviors of aqueous CaCl2 solutions via deep potential with electrostatic interactions. 深电位静电相互作用下CaCl2水溶液微结构和动力学行为的浓度依赖性研究。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0270174

Yunxiao Cui, Kaiwei Wan, Xinghua Shi

{"title":"Study of concentration dependent microstructures and dynamic behaviors of aqueous CaCl2 solutions via deep potential with electrostatic interactions.","authors":"Yunxiao Cui, Kaiwei Wan, Xinghua Shi","doi":"10.1063/5.0270174","DOIUrl":"https://doi.org/10.1063/5.0270174","url":null,"abstract":"Salt solutions have long been a subject of scientific interest owing to their significant role in various applications. Despite advances in experimental techniques and simulation methods, contradictions persist in describing the solvation structure and dynamic behavior of ions and water molecules in salt solutions, especially for non-monovalent salt solutions. In this study, we focus on the aqueous CaCl2 system and developed an advanced machine learning force field that incorporates electrostatic interactions, enabling high-accuracy molecular dynamics simulations at the SCAN functional level on nanosecond timescales. Benchmark tests confirmed that our model closely matches both density functional theory results and experimental data. Through comprehensive analysis, the concentration dependence of the microscopic structure and dynamics of CaCl2 solutions was revealed, highlighting significant effects arising from ion species. In addition, we performed the first high-precision infrared spectroscopy simulation of CaCl2 solutions, validating changes in hydrogen bond networks, ion solvation shells, and water molecule dynamics. Our results describe the dependence of solvation structure and diffusion behavior in CaCl2 solutions, offering the theoretical foundation for future research in this field.","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":"144955999","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

Geometry-originated universal relation for arbitrary convex hard particles. 任意凸硬粒子的几何起源普适关系。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0281216

Yuheng Yang, Duanduan Wan

引用次数: 0

Incorporating local step-size adaptivity into the no-U-turn sampler using Gibbs self-tuning. 利用吉布斯自调谐将局部步长自适应纳入无u型转弯采样器。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0280793

Nawaf Bou-Rabee, Bob Carpenter, Tore Selland Kleppe, Milo Marsden

引用次数: 0

Deterministic optimization of Jastrow factors. Jastrow因子的确定性优化。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0284106

Maria-Andreea Filip, Evelin Martine Corvid Christlmaier, J Philip Haupt, Daniel Kats, Pablo López Ríos, Ali Alavi

{"title":"Deterministic optimization of Jastrow factors.","authors":"Maria-Andreea Filip, Evelin Martine Corvid Christlmaier, J Philip Haupt, Daniel Kats, Pablo López Ríos, Ali Alavi","doi":"10.1063/5.0284106","DOIUrl":"https://doi.org/10.1063/5.0284106","url":null,"abstract":"Highly flexible Jastrow factors have found significant use in stochastic electronic structure methods such as variational Monte Carlo (VMC) and diffusion Monte Carlo, as well as in quantum chemical transcorrelated (TC) approaches, which have recently seen great success in generating highly accurate electronic energies using moderately sized basis sets. In particular, for the latter, the intrinsic noise in the Jastrow factor due to its optimization by VMC can pose a problem, especially when targeting weak (non-covalent) interactions. In this paper, we propose a deterministic alternative to VMC Jastrow optimization, based on minimizing the \"variance of the TC reference energy\" in a standard basis set. Analytic expressions for the derivatives of the TC Hamiltonian matrix elements are derived and implemented. This approach can be used to optimize the parameters in the Jastrow functions, either from scratch or to refine an initial VMC-based guess, to produce noise-free Jastrows in a reproducible manner. Applied to the first row of atoms and molecules, the results show that the method yields Slater-Jastrow wavefunctions whose variances are almost as low as those obtained from standard VMC variance optimization, but whose energies are lower and comparable to those obtained from energy-minimization VMC. We propose that the method can be used both in the context of the transcorrelated method and in standard VMC as a new way to optimize Jastrow functions.","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":"144955733","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

Effects of guest molecular occupancy and electric field on thermal conductivity of CO2 hydrates. 客分子占位和电场对CO2水合物导热性能的影响。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0286293

Yuan Li, Kaibin Xiong, Yongxiao Qu, Xiaoyu Shi, Zhisen Zhang, Jianyang Wu

{"title":"Effects of guest molecular occupancy and electric field on thermal conductivity of CO2 hydrates.","authors":"Yuan Li, Kaibin Xiong, Yongxiao Qu, Xiaoyu Shi, Zhisen Zhang, Jianyang Wu","doi":"10.1063/5.0286293","DOIUrl":"https://doi.org/10.1063/5.0286293","url":null,"abstract":"CO2 hydrate technology plays a pivotal role in carbon dioxide capture/storage, gas separation, and natural gas recovery from natural gas hydrates, while simultaneously serving as a cost-effective phase-change material for thermal energy storage. The thermal transport characteristics of CO2 hydrates are of particular importance in these promising applications. Here, the role of CO2 molecular occupancy and external electric fields on the thermal conductivity (κ) of sI-type CO2 hydrates is explored using equilibrium molecular dynamics simulations. Results reveal that increasing CO2 occupancy in large 51262 cages enhances κ by up to 27.2%, while small 512 cages contribute minimally (<1%). The water framework dominates heat transport (>90%), with CO2@51262 and CO2@512 cages contributing ∼17%-18% and <1%, respectively, mediated by synergistic host-guest interactions. External electric fields reduce κ by around 4%-5% due to enhanced low-frequency phonon localization in CO2 and intensified anharmonic scattering. Phonon analyses, including phonon density of states, phonon lifetime, phonon participation ratio, and spectral energy density, reveal that CO2 occupancy suppresses water lattice vibrations, while electric fields redistribute phonon modes, reducing delocalization. This work advances the fundamental understanding of thermal transport in hydrate systems.","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":"144955756","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

Modulating magneto-photoluminescence effects in 3D lead halide perovskites via halide-component dependent Rashba spin-orbit coupling. 利用卤化物组分依赖的Rashba自旋轨道耦合调制三维卤化铅钙钛矿中的磁光发光效应。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0284865

Zhen Wang, Jifan Xie, Jiayu Zheng, Yin Yan, Xiantong Tang, Yongjie Wang, Xianju Zhou, Hongqiang Zhu, Ruiheng Pan, Yangyang Dang

{"title":"Modulating magneto-photoluminescence effects in 3D lead halide perovskites via halide-component dependent Rashba spin-orbit coupling.","authors":"Zhen Wang, Jifan Xie, Jiayu Zheng, Yin Yan, Xiantong Tang, Yongjie Wang, Xianju Zhou, Hongqiang Zhu, Ruiheng Pan, Yangyang Dang","doi":"10.1063/5.0284865","DOIUrl":"https://doi.org/10.1063/5.0284865","url":null,"abstract":"Three-dimensional lead halide perovskites (3D LHPs) exhibit giant Rashba spin-orbit coupling (SOC) due to their inherent lattice asymmetry and heavy-metal composition; yet, the impact of Rashba SOC on the luminescence dynamic of 3D LHPs remains debated. Here, we utilize the magneto-photoluminescence (Magneto-PL) effects as an effective tool to reveal the underlying spin-related opto-physical process in 3D LHPs. We find that the magneto-PL effects of 3D LHPs CH3NH3Pb(Br/I/IxCl1-x)3 thin films are negative and tunable at room temperature, indicating the remarkable suppression of their PL emission intensity by magnetic fields. Moreover, the largest magneto-PL magnitude of -3.60% is realized in CH3NH3PbIxCl3-x thin film at a magnetic field strength of ±1 T; oppositely, in CH3NH3PbI3 thin film, it is merely -0.75%. Combining magneto-optical spectroscopy and crystallographic analysis of 3D LHP thin films, we attribute this phenomenon to the interplay of the Rashba SOC-driven spin mixing and Zeeman splitting between dark singlet and bright triplet excitons, promoting spin conversion from dark excitonic states to bright states. In addition, we demonstrate that the Rashba SOC is tunable and has a direct relationship with the crystalline phase transition and grain size by modifying halide-components, which leads to the halide-components dependent magneto-PL effects in 3D LHP thin films. This work paves the way for improving the luminescence property of opto-spintronics materials via modulating Rashba SOC.","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":"144955788","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

Levels of symmetry-adapted perturbation theory (SAPT). II. Convergence of interaction energy components. 对称适应摄动理论（SAPT）的水平。2。相互作用能量分量的收敛性。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0275311

Jeffrey B Schriber, Austin M Wallace, Daniel L Cheney, C David Sherrill

{"title":"Levels of symmetry-adapted perturbation theory (SAPT). II. Convergence of interaction energy components.","authors":"Jeffrey B Schriber, Austin M Wallace, Daniel L Cheney, C David Sherrill","doi":"10.1063/5.0275311","DOIUrl":"https://doi.org/10.1063/5.0275311","url":null,"abstract":"Symmetry-adapted perturbation theory (SAPT) is a valuable theoretical technique useful in quantifying intermolecular interaction energies in terms of four physically meaningful components: electrostatics, exchange-repulsion, induction/polarization, and London dispersion. We present a systematic analysis of the convergence of SAPT total and component energies with respect to the level of theory and basis set using an extended database of 4569 van der Waals dimer geometries. Our analysis supports the use of SAPT0/aug-cc-pVDZ over previously recommended sSAPT0/jun-cc-pVDZ as an economical level of SAPT. Our previous recommendations of SAPT2+/aug-cc-pVDZ and SAPT2+(3)δMP2/aug-cc-pVTZ as medium and high cost variants, respectively, remain unchanged. However, SAPT0/aug-cc-pVDZ and SAPT2+/aug-cc-pVDZ total interaction energies on average rely on error cancellations, so they should be used with caution when parameterizing SAPT-based force fields and intermolecular potentials. SAPT2+(3)/aug-cc-pVTZ shows quantitatively accurate component energies, making it the preferred choice for applications when feasible. Finally, we examine a focal point approximation that approaches the accuracy of SAPT2+(3)δMP2/aug-cc-pVTZ with a significantly reduced cost.","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":"144955811","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

Observation of thickness dependent anomalous spin filtration in MoS2 ultra-thin films. 二硫化钼超薄膜中厚度依赖性异常自旋过滤的观察。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-08-28 DOI: 10.1063/5.0284624

Abhinandan Kumar, Subrata Majumder

{"title":"Observation of thickness dependent anomalous spin filtration in MoS2 ultra-thin films.","authors":"Abhinandan Kumar, Subrata Majumder","doi":"10.1063/5.0284624","DOIUrl":"https://doi.org/10.1063/5.0284624","url":null,"abstract":"This study exposes novel spin filtering phenomena in ultra-thin MoS2 films deposited on indium tin oxide (ITO) substrates. The novelty lies in the explicit dependence of spin polarization and filtering efficiency on the film thickness. MoS2, a transition metal dichalcogenide, exhibits promising spintronic properties due to its intrinsic spin-orbit coupling and the potential to control spin orientation. We prepared MoS2 films of various thicknesses on ITO substrates and investigated their spin-filtering behavior using scanning tunneling spectroscopy (STS). Results reveal that the degree of spin polarization is highly sensitive to the MoS2 layer thickness, with ultra-thin films (4 nm) exhibiting reverse spin polarization compared to thicker films (10-15 nm). This spin flipping is attributed to the structural deformations in MoS2 thin films, such as twisting and folding, that break spatial symmetry and induce chirality. These chiral distortions modulate the electronic states and promote spin-selective transport in the crystal. The findings underscore the tunability of spin filtering in MoS2/ITO structures through geometric control, offering valuable insights for developing chirality-assisted spintronic devices.","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":"144955815","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