Determining minimum energy conical intersections by enveloping the seam: exploring ground and excited state intersections in coupled cluster theory

TL;DR

This paper introduces an algorithm to locate minimum energy conical intersections without needing nonadiabatic coupling vectors, using hypersurface enveloping to improve coupled cluster theory's application in photochemistry.

Contribution

The authors develop a novel method that locates conical intersections by energy minimization on enveloping hypersurfaces, avoiding complex coupling vector calculations.

Findings

The method successfully identifies ground and excited state intersections.

Coupled cluster singles and doubles accurately describes these intersections.

The approach improves stability and convergence in conical intersection optimization.

Abstract

Minimum energy conical intersections can be used to rationalize photochemical processes. In this Letter, we examine an algorithm to locate these structures that does not require the evaluation of nonadiabatic coupling vectors, showing that it minimizes the energy on hypersurfaces that envelop the intersection seam. By constraining the states to be separated by a small non-zero energy difference, the algorithm ensures that numerical artifacts and convergence problems of coupled cluster theory at conical intersections are not encountered during the optimization. In this way, we demonstrate for various systems that minimum energy conical intersections with the ground state are well described by the coupled cluster singles and doubles model, suggesting that coupled cluster theory may in some cases provide a good description of relaxation to the ground state in nonadiabatic dynamics simulations.