Construction of Quasi-diabatic Hamiltonians That Accurately Represent ab Initio Determined Adiabatic Electronic States Coupled by Conical Intersections for Systems on the Order of 15 Atoms. Application to Cyclopentoxide Photoelectron Detachment in the Full 39 Degrees of Freedom

Abstract

We present, for systems of moderate dimension, a fitting framework to construct quasi-diabatic Hamiltonians that accurately represent ab initio adiabatic electronic structure data including the effects of conical intersections. The framework introduced here minimizes the difference between the fit prediction and the ab initio data obtained in the adiabatic representation, which is singular at a conical intersection seam. We define a general and flexible merit function to allow arbitrary representations and propose a representation to measure the fit-ab initio difference at geometries near electronic degeneracies. A fit Hamiltonian may behave poorly in insufficiently sampled regions, in which case a machine learning theory analysis of the fit representation suggests a regularization to address the deficiency. Our fitting framework including the regularization is used to construct the full 39-dimensional coupled diabatic potential energy surfaces for cyclopentoxy relevant to cyclopentoxide photoelectron detachment.