Combined Self-Consistent-Field and Spin-Flip Tamm–Dancoff Density Functional Approach to Potential Energy Surfaces for Photochemistry

Abstract

We present a new approach to calculating potential energy surfaces for photochemical reactions by combining self-consistent-field calculations for single-reference ground and excited states with symmetry-corrected spin-flip Tamm–Dancoff approximation calculations for multireference electronic states. The method is illustrated by an application with the M05-2X exchange-correlation functional to <i>cis</i>–<i>trans</i> isomerization of the penta-2,4-dieniminium cation, which is a model (with three conjugated double bonds) of the protonated Schiff base of retinal. We find good agreement with multireference configuration interaction-plus-quadruples (MRCISD+Q) wave function calculations along three key paths in the strong-interaction region of the ground and first excited singlet states