Approximate Excited-State Geometry Optimization with the State-Averaged Adaptive Sampling Configuration Interaction Algorithm with Large Active Spaces.

Abstract

The selected configuration interaction (SCI) wave function is a useful approximation to the full configuration interaction (FCI) one. The adaptive sampling CI (ASCI) method is a deterministic SCI method. By combining ASCI and orbital optimization, the ASCI self-consistent field (ASCI-SCF) method, which is an approximation of the complete active space self-consistent field (CASSCF) method, can be formulated as well. However, their applicability has been tested mainly on the systems in their electronically ground states. In this work, we implement the state-average (SA) ansatz in ASCI-SCF calculations to calculate excited states. We also derive expressions for the approximate analytical gradient and implement them as a computer program. We demonstrate the applicability of the current method for calculating vertical and adiabatic excitation energies and optimizing the molecular geometries of thermally activated delayed fluorescence (TADF) molecules.