Ehrenfest 方法与完全量子核运动（Qu-Eh）：在自由基阳离子中电荷迁移的应用。

The Ehrenfest method with fully quantum nuclear motion (Qu-Eh): Application to charge migration in radical cations.

机构信息

Department of Chemistry, University of Washington, Seattle, Washington 98195, USA.

Department of Chemistry, University College London, 20, Gordon St., WC1H 0AJ London, United Kingdom.

出版信息

J Chem Phys. 2018 Sep 7;149(9):094108. doi: 10.1063/1.5038428.

DOI:10.1063/1.5038428

PMID:30195291

Abstract

An algorithm is described for quantum dynamics where an Ehrenfest potential is combined with fully quantum nuclear motion (Quantum-Ehrenfest, Qu-Eh). The method is related to the single-set variational multi-configuration Gaussian approach (vMCG) but has the advantage that only a single quantum chemistry computation is required at each time step since there is only a single time-dependent potential surface. Also shown is the close relationship to the "exact factorization method." The quantum Ehrenfest method is compared with vMCG for study of electron dynamics in a modified bismethylene-adamantane cation system. Illustrative examples of electron-nuclear dynamics are presented for a distorted allene system and for HCCI where one has a degenerate Π system.

摘要

描述了一种量子动力学算法，其中 Ehrenfest 势与完全量子核运动相结合（量子 Ehrenfest，Qu-Eh）。该方法与单集变分多组态高斯方法（vMCG）有关，但具有优势，即在每个时间步只需要进行一次量子化学计算，因为只有一个时间相关的势能面。还显示了与“精确分解方法”的紧密关系。将量子 Ehrenfest 方法与 vMCG 进行比较，以研究改良的双亚甲基-金刚烷阳离子系统中的电子动力学。给出了一个扭曲的烯丙基系统和 HCCI 的电子-核动力学示例，其中一个系统是简并的Π系统。