与电子和空穴传输问题相关的受约束 CASSCF(1,2) 和 CASSCF(3,2) 模拟的高效算法

IF 5.7 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2024-10-07 DOI:10.1021/acs.jctc.4c00937

Tian Qiu, Joseph E. Subotnik

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引用次数: 0

摘要

我们为最近发表的电子/空穴传输动态加权状态平均约束CASSCF（eDSC/hDSC）方法提出了一种高效算法，用于研究奇数电子系统的电荷转移态和D1-D0交叉。通过将约束最小化问题分离为无约束自洽场（SCF）问题和约束非自洽场（nSCF）问题，以及加速迭代子空间直接反演（DIIS）技术来解决 SCF 问题，与直接使用序列二次编程（SQP）相比，总体计算成本降低了 8-20 倍。这种方法应适用于其他受约束的最小化问题，而且在不久的将来，一旦梯度可用，目前的 eDSC/hDSC 算法应能实现快速的非绝热动力学模拟。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

An Efficient Algorithm for Constrained CASSCF(1,2) and CASSCF(3,2) Simulations as Relevant to Electron and Hole Transfer Problems

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An Efficient Algorithm for Constrained CASSCF(1,2) and CASSCF(3,2) Simulations as Relevant to Electron and Hole Transfer Problems

We propose an efficient algorithm for the recently published electron/hole-transfer Dynamical-weighted State-averaged Constrained CASSCF (eDSC/hDSC) method studying charge transfer states and D₁-D₀ crossings for systems with odd numbers of electrons. By separating the constrained minimization problem into an unconstrained self-consistent-field (SCF) problem and a constrained nonself-consistent-field (nSCF) problem, as well as accelerating the direct inversion in the iterative subspace (DIIS) technique to solve the SCF problem, the overall computational cost is reduced by a factor of 8–20 compared with directly using sequential quadratic programming (SQP). This approach should be applicable for other constrained minimization problems, and in the immediate future, once gradients are available, the present eDSC/hDSC algorithm should allow for speedy nonadiabatic dynamics simulations.

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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Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere.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.