Complete active space and corrected density functional theories helping each other to describe vertical electronic π → π* excitations in prototype multiple-bonded molecules.

Abstract

The CASΠDFT method, which combines the complete active space (CAS) wave function approach and density functional theory (DFT), offers an efficient description of important excitations to the lowest excited states. CASΠDFT employs a correlation DFT functional corrected with a function P[x] of the ratio xr of the conditional and conventional electron densities obtained with the CAS on-top pair density Π(r). The sectors of P[x] for x(r) ≤ 1 and x(r) > 1 represent the opposite effects of the suppression of dynamic correlation with nondynamic correlation and its enhancement due to the ionic-type excitation. The present combination of the self-consistent-field CAS and the corrected Lee-Yang-Parr correlation functional closely reproduces in the relatively small double-zeta basis the benchmark experimental lowest singlet vertical π → π* excitations in the prototype multiple-bonded molecules N2, CO, C2H2, and C2H4.