Journal of Chemical Physics最新文献

The evolution of the Amber additive protein force field: History, current status, and future. 琥珀添加剂蛋白力场的演变：历史、现状和未来。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-21 DOI: 10.1063/5.0227517

Xianwei Wang, Danyang Xiong, Yueqing Zhang, Jihang Zhai, Yu-Cheng Gu, Xiao He

引用次数: 0

Kohn-Sham inversion for open-shell systems. 开壳系统的Kohn-Sham反演。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-21 DOI: 10.1063/5.0239422

Jannis Erhard, Egor Trushin, Andreas Görling

{"title":"Kohn-Sham inversion for open-shell systems.","authors":"Jannis Erhard, Egor Trushin, Andreas Görling","doi":"10.1063/5.0239422","DOIUrl":"https://doi.org/10.1063/5.0239422","url":null,"abstract":"Methods based on density-functional theory usually treat open-shell atoms and molecules within the spin-unrestricted Kohn-Sham (KS) formalism, which breaks symmetries in real and spin space. Symmetry breaking is possible because the KS Hamiltonian operator does not need to exhibit the full symmetry of the physical Hamiltonian operator, but only the symmetry of the spin density, which is generally lower. Symmetry breaking leads to spin contamination and prevents a proper classification of the KS wave function with respect to the symmetries of the physical electron system. Formally well-justified variants of the KS formalism that restore symmetries in real space, in spin space, or in both have been introduced long ago, but have rarely been used in practice. Here, we introduce numerically stable KS inversion methods to construct reference KS potentials from reference spin-densities for all four possibilities to treat open shell systems, non-symmetrized, spin-symmetrized, space-symmetrized, and fully-symmetrized. The reference spin-densities are obtained by full configuration interaction and high-level coupled cluster methods for the considered atoms and diatomic molecules. The decomposition of the total energy in contributions such as the non-interacting kinetic, the exchange, and the correlation energy is different in the four KS formalisms. Reference values for these differences are provided for the considered atoms and molecules. All KS inversions, except the fully symmetrized one, lead in some cases to solutions violating the Aufbau principle. In the purely spin-symmetrized KS formalism, this represents a violation of the KS v-representability condition, i.e., no proper KS wave functions exist in those cases.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143006131","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 divide expand consolidate scheme for unrestricted second order Møller-Plesset perturbation theory ground state energies. 无限制二阶Møller-Plesset微扰理论基态能量的分展巩固方案。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-21 DOI: 10.1063/5.0228963

Magnus Bukhave Johansen, Andreas Erbs Hillers-Bendtsen, Hector H Corzo, Ashleigh Barnes, Kurt V Mikkelsen, Dmytro Bykov

{"title":"The divide expand consolidate scheme for unrestricted second order Møller-Plesset perturbation theory ground state energies.","authors":"Magnus Bukhave Johansen, Andreas Erbs Hillers-Bendtsen, Hector H Corzo, Ashleigh Barnes, Kurt V Mikkelsen, Dmytro Bykov","doi":"10.1063/5.0228963","DOIUrl":"https://doi.org/10.1063/5.0228963","url":null,"abstract":"The linear scaling divide-expand-consolidate (DEC) framework is expanded to include unrestricted Hartree-Fock references. By partitioning the orbital space and employing local molecular orbitals, the full molecular calculation can be performed as independent calculations on individual fragments, making the method well-suited for massively parallel implementations. This approach also incorporates error control through the fragment optimization threshold (FOT), which maintains precision and consistency throughout the calculations. A benchmark was conducted for correlation energies of open-shell systems and the relative energies of both open- and closed-shell molecules at the MP2 level of theory. The full calculation result is achieved as the FOT approaches zero. For correlation energies, an FOT of 10-3 is sufficient to recover over 98% of the full result in all cases. However, for relative energies and the electronic energy component of oxidation potentials, a tighter FOT of 10-4 is required to keep the DEC error within 10% for both open- and closed-shell molecules. This is likely due to a lack of systematic error cancellation for the molecules with vastly different chemical natures. Therefore, for accurate relative energies, the FOT should be an order of magnitude lower, and additional caution is needed, particularly for large systems. The DEC method extension to unrestricted references maintains favorable features of linear scaling and can be implemented in a massively parallel algorithm to calculate correlation energies for large open-shell systems.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143006054","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

Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons. 集体旋转振动极化子动力学和光谱的从头算研究。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-21 DOI: 10.1063/5.0244977

Tamás Szidarovszky

引用次数: 0

The orientational structure of a model patchy particle fluid: Simulations, integral equations, density functional theory, and machine learning. 斑片状粒子流体模型的取向结构：模拟、积分方程、密度泛函理论和机器学习。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-21 DOI: 10.1063/5.0248694

Alessandro Simon, Luc Belloni, Daniel Borgis, Martin Oettel

{"title":"The orientational structure of a model patchy particle fluid: Simulations, integral equations, density functional theory, and machine learning.","authors":"Alessandro Simon, Luc Belloni, Daniel Borgis, Martin Oettel","doi":"10.1063/5.0248694","DOIUrl":"https://doi.org/10.1063/5.0248694","url":null,"abstract":"We investigate the orientational properties of a homogeneous and inhomogeneous tetrahedral four-patch fluid (Bol-Kern-Frenkel model). Using integral equations, either (i) HNC or (ii) a modified HNC scheme with a simulation input, the full orientational dependence of pair and direct correlation functions is determined. Density functionals for the inhomogeneous problem are constructed via two different methods. The first, molecular density functional theory, utilizes the full direct correlation function and an isotropic hard-sphere bridge functional. The second method, a machine learning approach, uses a decomposition of the functional into an isotropic reference part and a mean-field orientational part, where both parts are improved by machine learning techniques. A comparison with the simulation data at hard walls and around hard tracers shows a similar performance of the two functionals. Machine learning strategies are discussed to eliminate residual differences, with the goal of obtaining machine-learning enhanced functionals for the general anisotropic fluid.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 3","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143006057","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

Highly accurate real-space electron densities with neural networks. 高度精确的真实空间电子密度与神经网络。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-21 DOI: 10.1063/5.0236919

Lixue Cheng, P Bernát Szabó, Zeno Schätzle, Derk P Kooi, Jonas Köhler, Klaas J H Giesbertz, Frank Noé, Jan Hermann, Paola Gori-Giorgi, Adam Foster

引用次数: 0

pyVPT2: Interoperable software for anharmonic vibrational frequency calculations. pyVPT2：用于非谐波振动频率计算的可互操作软件。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-21 DOI: 10.1063/5.0251445

Philip M Nelson, C David Sherrill

引用次数: 0

Mpemba effect in the relaxation of an active Brownian particle in a trap without metastable states. 无亚稳态阱中活性布朗粒子弛豫的Mpemba效应。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-21 DOI: 10.1063/5.0246857

Apurba Biswas, R Rajesh

引用次数: 0

A computational study on the effect of structural isomerism on the excited state lifetime and redox energetics of archetype iridium photoredox catalyst platforms [Ir(ppy)2(bpy)]+ and Ir(ppy)3. 结构异构对原型铱光氧化还原催化剂平台[Ir(ppy)2(bpy)]+和Ir(ppy)3激发态寿命和氧化还原能量影响的计算研究。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-14 DOI: 10.1063/5.0239293

Daniel Gómez Bustos, Sreeprasad Sreenivasan, Balazs Pinter

{"title":"A computational study on the effect of structural isomerism on the excited state lifetime and redox energetics of archetype iridium photoredox catalyst platforms [Ir(ppy)2(bpy)]+ and Ir(ppy)3.","authors":"Daniel Gómez Bustos, Sreeprasad Sreenivasan, Balazs Pinter","doi":"10.1063/5.0239293","DOIUrl":"https://doi.org/10.1063/5.0239293","url":null,"abstract":"This study investigates the impact of structural isomerism on the excited state lifetime and redox energetics of heteroleptic [Ir(ppy)2(bpy)]+ and homoleptic Ir(ppy)3 photoredox catalysts using ground-state and time-dependent density functional theory methods. While the ground- and excited-state reduction potentials differ only slightly among the isomers of these complexes, our findings reveal significant variations in the radiative and non-radiative decay rates of the reactivity-controlling triplet 3MLCT states of these closely related species. The observed differences in radiative decay rates could be traced back to variations in the transition dipole moment, vertical energy gaps, and spin-orbit coupling of the isomers. In [Ir(ppy)2(bpy)]+, transition dipole moment differences play a significant role in controlling the relative lifetime of the triplet states, which we rationalized by a vectorial analysis of permanent dipole moments of the ground and excited states. Regarding the two isomers of Ir(ppy)3, changes in radiative decay rates were primarily attributed to variations in vertical energy gaps and intensity borrowing from other singlet-singlet transitions driven by spin-orbit coupling. Non-radiative decay variations were assessed in terms of differences in reorganization energies, adiabatic energy gap, and spin-orbit coupling. For both complexes, reorganization energies associated with low-energy molecular vibrations and metal-ligand bond length changes following the de-excitation process were major contributors. These insights provide a deeper understanding of how molecular design can be leveraged to optimize the performance of iridium-based photoredox catalysts, potentially guiding the development of more efficient catalytic systems for future applications.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142978569","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

Accurate machine learning of rate coefficients for state-to-state transitions in molecular collisions. 分子碰撞中状态到状态转换速率系数的精确机器学习。

IF 3.1 2区化学

Journal of Chemical Physics Pub Date : 2025-01-14 DOI: 10.1063/5.0242182

Darin E Mihalik, R Wang, B H Yang, P C Stancil, T J Price, R C Forrey, N Balakrishnan, R V Krems

{"title":"Accurate machine learning of rate coefficients for state-to-state transitions in molecular collisions.","authors":"Darin E Mihalik, R Wang, B H Yang, P C Stancil, T J Price, R C Forrey, N Balakrishnan, R V Krems","doi":"10.1063/5.0242182","DOIUrl":"https://doi.org/10.1063/5.0242182","url":null,"abstract":"We present an algorithm that combines quantum scattering calculations with probabilistic machine-learning models to predict quantum dynamics rate coefficients for a large number of state-to-state transitions in molecule-molecule collisions much faster than with direct solutions of the Schrödinger equation. By utilizing the predictive power of Gaussian process regression with kernels, optimized to make accurate predictions outside of the input parameter space, the present strategy reduces the computational cost by about 75%, with an accuracy within 5%. Our method uses temperature dependences of rate coefficients for transitions from the isolated states of initial rotational angular momentum j, determined via explicit calculations, to predict the temperature dependences of rate coefficients for other values of j. The approach, demonstrated here for rovibrational transitions of SiO due to thermal collisions with H2, uses different prediction models and is thus adaptive to various time and accuracy requirements. The procedure outlined in this work can be used to extend multiple inelastic molecular collision databases without exponentially large computational resources required for conventional rigorous quantum dynamics calculations.","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"162 2","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142978581","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