激发态之间的一阶非绝热耦合矩阵元：在含时密度泛函理论（TD-DFT）和含时极化偶极近似（pp-TDA）水平下的实现与应用

First order nonadiabatic coupling matrix elements between excited states: implementation and application at the TD-DFT and pp-TDA levels.

作者信息

Li Zhendong, Suo Bingbing, Liu Wenjian

机构信息

Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistryand Molecular Engineering, and Center for Computational Science and Engineering, Peking University, Beijing 100871, People's Republic of China.

出版信息

J Chem Phys. 2014 Dec 28;141(24):244105. doi: 10.1063/1.4903986.

DOI:10.1063/1.4903986

PMID:25554131

Abstract

The recently proposed rigorous yet abstract theory of first order nonadiabatic coupling matrix elements (fo-NACME) between electronically excited states [Z. Li and W. Liu, J. Chem. Phys. 141, 014110 (2014)] is specified in detail for two widely used models: The time-dependent density functional theory and the particle-particle Tamm-Dancoff approximation. The actual implementation employs a Lagrangian formalism with atomic-orbital based direct algorithms, which makes the computation of fo-NACME very similar to that of excited-state gradients. Although the methods have great potential in investigating internal conversions and nonadiabatic dynamics between excited states of large molecules, only prototypical systems as a first pilot application are considered here to illustrate some conceptual aspects.

摘要

最近提出的关于电子激发态之间一阶非绝热耦合矩阵元（fo-NACME）的严格但抽象的理论[Z. Li和W. Liu，《化学物理杂志》141, 014110 (2014)]针对两种广泛使用的模型进行了详细阐述：含时密度泛函理论和粒子-粒子Tamm-Dancoff近似。实际实现采用了基于原子轨道直接算法的拉格朗日形式，这使得fo-NACME的计算与激发态梯度的计算非常相似。尽管这些方法在研究大分子激发态之间的内转换和非绝热动力学方面具有很大潜力，但这里仅考虑典型系统作为首次试点应用，以说明一些概念性方面。