Excited state surfaces in density functional theory: A new twist on an old problem

Excited state surfaces in density functional theory and the problem of charge transfer are considered from an orbital overlap perspective. For common density functional approximations, the accuracy of the surface will not be uniform if the spatial overlap between the occupied and virtual orbitals involved in the excitation has a strong conformational dependence; the excited state surface will collapse toward the ground state in regions where the overlap is very low. This characteristic is used to predict and to provide insight into the breakdown of excited state surfaces in the classic push-pull 4-(dimethylamino)benzonitrile molecule, as a function of twist angle. The breakdown is eliminated using a Coulomb-attenuated functional. Analogous situations will arise in many molecules.