The Construction of Semi-diabatic Potential Energy Surfaces of Excited States for Use in Excited State AIMD Studies by the Equation-of-Motion Coupled-Cluster Method

摘要

The semi-diabatic potential energy surfaces (PESs) of the excited states of polyatomic molecules can be constructed for use in ab initio molecular dynamics (AIMD) studies by relying on the continuity of the electronic energy, oscillator strength, and spherical extent of an excited state along with first derivatives of these quantities as computed by using the equation-of-motion coupled-cluster (EOM-CC) method. The semidiabatic PESs of both the p? p* valence excited state and the 3s-type Rydberg state of ethylene are presented and discussed in this paper, in conjunction with some of the AIMD results we obtained for these states.