Zhaoyong Li, Chaoqun Zhang, Yifan Shen, Linjun Wang
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引用次数: 0
摘要
由于绝热势能面(PES)的尖顶脊和非绝热耦合(NAC)的奇异性,很难获得绝热哈密顿的解析表达式。因此,非绝热动力学模拟通常是即时进行的,非常耗时。这促使我们构建具有平滑 PES 和绝热耦合的准绝热表示。在本研究中,我们提出了一种基于有限构型空间中最小化导数耦合(MDC)的新准二绝热化方法。首先考虑边界条件,最后释放边界条件,得到绝热-绝热旋转角和变换矩阵。正如在具有代表性的一维和二维模型以及广泛研究的线性 H3 分子中所证明的那样,MDC 的性能明显优于直接积分准二绝热化方法。特别是,即使考虑空间中所有构型的 NAC 都不可忽略,也能成功获得精确的二重化势能矩阵。
Quasi-Diabatization Based on Minimizing Derivative Couplings in a Limited Configuration Space: Elimination of Boundary Condition Dependence
Due to the cuspidal ridges of adiabatic potential energy surfaces (PESs) and singularities of nonadiabatic couplings (NACs), obtaining an analytical expression for the adiabatic Hamiltonian is difficult. Thereby, nonadiabatic dynamics simulations are often carried out on-the-fly, which is time-consuming. This motivates us to construct quasi-diabatic representations, which have smooth PESs and diabatic couplings. In this study, we propose a new quasi-diabatization method based on minimizing derivative couplings (MDC) in a limited configuration space. The boundary conditions are first considered and finally released to obtain the adiabatic-to-diabatic rotation angles and transformation matrices. As demonstrated in representative one- and two-dimensional models and the widely studied linear H3 molecule, MDC performs significantly better than the direct integration quasi-diabatization approach. In particular, accurate diabatic potential energy matrices have been successfully obtained even when the NACs of all configurations in the considered space are nonnegligible.
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.