Zhaoyong Li, Chaoqun Zhang, Yifan Shen, Linjun Wang
{"title":"Quasi-Diabatization Based on Minimizing Derivative Couplings in a Limited Configuration Space: Elimination of Boundary Condition Dependence","authors":"Zhaoyong Li, Chaoqun Zhang, Yifan Shen, Linjun Wang","doi":"10.1021/acs.jpclett.4c02557","DOIUrl":null,"url":null,"abstract":"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 H<sub>3</sub> 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.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry Letters","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpclett.4c02557","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
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.