Analytic First-Order Derivatives of CASPT2 Combined with the Polarizable Continuum Model

IF 5.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2025-01-16 DOI:10.1021/acs.jctc.4c0147310.1021/acs.jctc.4c01473

Yoshio Nishimoto*,

引用次数: 0

Abstract

The complete active space second-order perturbation theory (CASPT2) is valuable for accurately predicting electronic structures and transition energies. However, optimizing molecular geometries in the solution phase has proven challenging. In this study, we develop analytic first-order derivatives of CASPT2 using an implicit solvation model, specifically the polarizable continuum model, within the open-source package OpenMolcas. Analytic gradients and nonadiabatic coupling vectors are computed by solving a modified Z-vector equation. Comparisons with existing theoretical and experimental results demonstrate that the solvent effects can be qualitatively captured using the developed method.

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结合可极化连续体模型的CASPT2一阶解析导数

完全有源空间二阶摄动理论（CASPT2）对于准确预测电子结构和跃迁能具有重要意义。然而，在溶液阶段优化分子几何形状已被证明是具有挑战性的。在这项研究中，我们使用隐式溶剂化模型，特别是极化连续体模型，在开源软件包OpenMolcas中开发了CASPT2的解析一阶导数。解析梯度和非绝热耦合矢量通过求解修正的z矢量方程来计算。与已有的理论和实验结果比较表明，该方法可以定性地捕捉溶剂效应。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Chemical Theory and Computation 化学-物理：原子、分子和化学物理

CiteScore

9.90

自引率

16.40%

发文量

568

审稿时长

1 months

期刊介绍： The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.