Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach

Abstract

A time-independent density functional approach to the calculation of excitation energies from the ground states of molecules typified by the strong nondynamic electron correlation is suggested. The new method is based on the use of the spin-restricted ensemble-referenced Kohn-Sham formalism [Filatov, M.; Shaik, S. Chem. Phys. Lett. 1999, 304, 429] for the calculation of the ground state. In the new method, the average energy of the ground state and a state created by a single excitation thereof is minimized with respect to the Kohn-Sham orbitals and their fractional occupation numbers. The lowest singlet excitation energies obtained with the help of the new formalism for a number of model systems, such as the hydrogen molecule with stretched bond, twisted ethylene, and twisted hexa-1,3,5-triene, are compared with the results of the time-dependent density functional theory, with the results of ab initio CASSCF/CASPT2 calculations, and with the experimental data. Applicability of the new method to the description of photochemical reactions is discussed.