Diabatic States of Molecules

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2022-02, Vol.126 (7), p.992-1018
• Main Authors: Shu, Yinan, Varga, Zoltan, Kanchanakungwankul, Siriluk, Zhang, Linyao, Truhlar, Donald G
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.1c10583

Quantitative simulations of electronically nonadiabatic molecular processes require both accurate dynamics algorithms and accurate electronic structure information. Direct semiclassical nonadiabatic dynamics is expensive due to the high cost of electronic structure calculations, and hence it is limited to small systems, limited ensemble averaging, ultrafast processes, and/or electronic structure methods that are only semiquantitatively accurate. The cost of dynamics calculations can be made manageable if analytic fits are made to the electronic structure data, and such fits are most conveniently carried out in a diabatic representation because the surfaces are smooth and the couplings between states are smooth scalar functions. Diabatic representations, unlike the adiabatic ones produced by most electronic structure methods, are not unique, and finding suitable diabatic representations often involves time-consuming nonsystematic diabatization steps. The biggest drawback of using diabatic bases is that it can require large amounts of effort to perform a globally consistent diabatization, and one of our goals has been to develop methods to do this efficiently and automatically. In this Feature Article, we introduce the mathematical framework of diabatic representations, and we discuss diabatization methods, including adiabatic-to-diabatic transformations and recent progress toward the goal of automatization.