Diabatization by Machine Intelligence.

Abstract

Understanding nonadiabatic dynamics is important for chemical and physical processes involving multiple electronic states. Direct nonadiabatic dynamics simulations are often employed to observe such processes on a femtosecond time scale. One often needs to do the simulation on a longer time scale, but direct simulation based on electronic structure calculations of the surfaces and couplings is expensive due to the large number of electronic structure calculations needed for ensemble averaging or simulation of longer-time processes. An alternative approach is to construct an analytical representation of potential energy surfaces (PESs) and couplings, which allows for faster dynamics calculations. Diabatic representations are preferred for such purposes because of the smoothness of the surfaces and couplings and the scalar nature of the couplings. However, many diabatization procedures are complicated by the need to consider orbitals or vector coupling elements, and these can make the process very labor-intensive. To circumvent these difficulties, we here propose diabatization by a deep neural network (DDNN) based on a new architecture for a deep neural network that requires neither orbital input nor vector input. The DDNN method allows convenient and semiautomatic diabatization, and it is demonstrated here for a model problem and for producing diabatic potential energy matrices for thiophenol.