New Gradient Correction Scheme for Electronically Nonadiabatic Dynamics Involving Multiple Spin States

• DOI: 10.1021/acs.jctc.2c01173
• Publication Date: 2023-04-20T20:05:05Z
• Authors: Yinan Shu; Linyao Zhang; Dihua Wu; Xiye Chen; Shaozeng Sun; Donald G. Truhlar
• Keywords: Intersystem crossing; Surface hopping; Hamiltonian (control theory); Basis (linear algebra); Basis function; Vibronic coupling

It has been recommended that the best representation to use for trajectory surface hopping (TSH) calculations is fully adiabatic basis in which Hamiltonian diagonal. Simulations of intersystem crossing processes with conventional TSH methods require an explicit computation nonadiabatic coupling vectors (NACs) molecular-Coulomb-Hamiltonian (MCH) basis, also called spin-orbit-free order compute gradient (also diagonal representation). This requirement destroys some advantages overlap-based algorithms and curvature-driven can be used most efficient calculations. Therefore, although these allow one perform NAC-free simulations internal conversion processes, still requires NACs crossing. Here, we show how NAC circumvented by a new scheme time-derivative-matrix scheme.