English

A Simple One-Electron Expression for Electron Rotational Factors

Computational Physics 2024-01-26 v1

Abstract

Within the context of FSSH dynamics, one often wishes to remove the angular component of the derivative coupling between states J>\left|J\right> and K>\left|K\right>. In a set of previous papers, Truhlar {\em et al.} posited one approach for such a removal based on direct projection, while we isolated a second approach by constructing and differentiating rotationally invariant basis. Unfortunately, neither approach was able to demonstrate a {\em one-electron operator} O^\hat{O} whose matrix element <JO^K>\left<J|\hat{O}|K\right> was the angular component of the derivative coupling. Here, we show that a one-electron operator can in fact be constructed efficiently in a semi-local fashion. The present results yield physical insight into designing new surface hopping algorithms and be of immediate use for FSSH calculations.

Cite

@article{arxiv.2401.13778,
  title  = {A Simple One-Electron Expression for Electron Rotational Factors},
  author = {Tian Qiu and Mansi Bhati and Zhen Tao and Xuezhi Bian and Jonathan Rawlinson and Robert G. Littlejohn and Joseph E. Subotnik},
  journal= {arXiv preprint arXiv:2401.13778},
  year   = {2024}
}
R2 v1 2026-06-28T14:26:21.143Z