Analytical gradients and derivative couplings for dynamically weighted complete active space self-consistent field.

Abstract

We recently introduced a Dynamically Weighted Complete Active Space Self-Consistent Field (DW-CASSCF) electronic structure for excited-state dynamics. In this Communication, we reformulate analytical gradients at this level of theory using a Lagrangian approach, thereby reducing the required number of coupled-perturbed CASSCF calculations to one per state gradient. In addition, we derive and implement derivative couplings at the DW-CASSCF level for the first time. We demonstrate the new formulation of DW-CASSCF gradients by optimizing a conical intersection for the p-hydroxybenzylidene-imidazolinone anion, the green fluorescent protein chromophore, to shed light on its observed radiationless decay dynamics in the ultraviolet region.