Optimizing Conical Intersections without Explicit Use of Non-Adiabatic Couplings

Abstract

We present two alternative methods for optimizing minimum energy conical intersection (MECI) molecular geometries without knowledge of the derivative coupling (DC). These methods are based on the utilization of Lagrange multipliers: (i) one method uses an approximate calculation of the DC, while the other (ii) do not require the DC. Both methods use the fact that information on the DC is contained in the Hessian of the squared energy difference. Tests done on a set of small molecular systems, in comparison with other methods, show the ability of the proposed methods to optimize MECIs. Finally, we apply the methods to the furimamide molecule, to optimize and characterize its S 1 /S 2 MECI, and to optimizing the S 0 /S 1 MECI of the silver trimer.