Comparison of Spin-Flip TDDFT-Based Conical Intersection Approaches with XMS-CASPT2

Abstract

Determining conical intersection geometries is of key importance to understanding the photochemical reactivity of molecules. While many small- to medium-sized molecules can be treated accurately using multireference approaches, larger molecules require a less computationally demanding approach. In this work, minimum energy crossing point conical intersection geometries for a series of molecules have been studied using spin-flip TDDFT (SF-TDDFT), within the Tamm-Dancoff Approximation, both with and without explicit calculation of nonadiabatic coupling terms, and compared with both XMS-CASPT2 and CASSCF calculated geometries. The less computationally demanding algorithms, which do not require explicit calculation of the nonadiabatic coupling terms, generally fare well with the XMS-CASPT2 reference structures, while the relative energetics are only reasonably replicated with the MECP structure as calculated with the BHHLYP functional and full nonadiabatic coupling terms. We also demonstrate that, occasionally, CASSCF structures deviate quantitatively from the XMS-CASPT2 structures, showing the importance of including dynamical correlation.