Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules

ABSTRACT: A number of commonly available density functionals have been tested for their ability to describe the energetics and the geometry at conical intersections in connection with the spin-restricted ensemble referenced Kohn−Sham (REKS) method. The minimum energy conical intersections have been optimized for several molecular systems, which are widely used as paradigmatic models of photochemical rearrangements and models of biological chromophores. The results of the calculations are analyzed using the sign-change theorem of Longuet-Higgins and a method of elementary reaction coordinates of Haas et al. The latter approach helps to elucidate the differences between the geometries at conical intersections as predicted by the multireference wave function ab initio methods and by the density functional methods. Overall, the BH&HLYP density functional yields the best results for the conical intersection geometries and energetics. 1