Impact of Dipole Self-Energy on Cavity-Induced Nonadiabatic Dynamics

IF 5.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2025-01-07 DOI:10.1021/acs.jctc.4c0145410.1021/acs.jctc.4c01454

Csaba Fábri*, Gábor J. Halász, Jaroslav Hofierka, Lorenz S. Cederbaum and Ágnes Vibók*,

引用次数: 0

Abstract

The coupling of matter to the quantized electromagnetic field of a plasmonic or optical cavity can be harnessed to modify and control chemical and physical properties of molecules. In optical cavities, a term known as the dipole self-energy (DSE) appears in the Hamiltonian to ensure gauge invariance. The aim of this work is twofold. First, we introduce a method, which has its own merits and complements existing methods, to compute the DSE. Second, we study the impact of the DSE on cavity-induced nonadiabatic dynamics in a realistic system. For that purpose, various matrix elements of the DSE are computed as functions of the nuclear coordinates and the dynamics of the system after laser excitation is investigated. The cavity is known to induce conical intersections between polaritons, which gives rise to substantial nonadiabatic effects. The DSE is shown to slightly affect these light-induced conical intersections and, in particular, break their symmetry.

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偶极自能对空腔诱导非绝热动力学的影响

物质与等离子体或光学腔的量子化电磁场的耦合可以用来修饰和控制分子的化学和物理性质。在光学腔中，一个称为偶极自能（DSE）的术语出现在哈密顿量中以确保规范不变性。这项工作的目的是双重的。首先，我们介绍了一种具有自身优点并与现有方法相辅相成的计算DSE的方法。其次，我们研究了一个实际系统中DSE对空腔诱导非绝热动力学的影响。为此，计算了DSE的各种矩阵元素作为核坐标的函数，并研究了激光激发后系统的动力学。已知该空腔可诱导极化之间的锥形相交，从而产生大量的非绝热效应。结果表明，DSE对这些光诱导的锥形相交有轻微的影响，特别是破坏了它们的对称性。

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Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere.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