A Complete Active Space Self-Consistent Field Approach for Molecules in QED Environments.

IF 5.7 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2025-07-22 Epub Date: 2025-07-07 DOI:10.1021/acs.jctc.5c00519

Riccardo Alessandro, Matteo Castagnola, Henrik Koch, Enrico Ronca

引用次数: 0

Abstract

Multireference systems are usually challenging to investigate using ab initio methods as they require an accurate description of static electron correlation. The urgency of developing similar approaches is even more pressing when molecules strongly interact with light in quantum-electrodynamics (QED) environments. In fact, in this context, multireference effects might be induced or reduced by the presence of the field. In this work, we extend the complete active space self-consistent field (CASSCF) approach to polaritonic systems. The method is tested on benchmark multireference problems and applied to investigate field-induced effects on the electronic structure of well-known multiconfigurational processes. Strengths and limitations of the method have been thoroughly analyzed.

查看原文本刊更多论文

QED环境中分子的完全主动空间自洽场方法。

使用从头算方法研究多参考系统通常具有挑战性，因为它们需要精确描述静态电子相关性。当分子在量子电动力学（QED）环境中与光强烈相互作用时，开发类似方法的紧迫性就更加紧迫了。事实上，在这种情况下，多参考效应可能会因磁场的存在而引起或减弱。在这项工作中，我们将完全有源空间自洽场（CASSCF）方法扩展到极化系统。该方法在基准多参考问题上进行了测试，并应用于研究众所周知的多组态过程的场致电子结构影响。对该方法的优点和局限性进行了深入分析。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

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Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere.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