Molecular multibond dissociation with small complete active space augmented by correlation density functionals.

Abstract

Molecular multibond dissociation displays a variety of electron correlation effects posing a challenge for theoretical description. We propose a CASΠ(M)DFT approach, which includes these effects in an efficient way by combining the complete active space self-consistent field method with density functional theory (DFT). Within CASΠ(M)DFT, a small complete active space (CAS) accounts for the long-range intrabond and middle-range interbond nondynamic correlation in the stretched bonds. The common short-range dynamic correlation is calculated with the Lee-Yang-Parr (LYP) correlation DFT functional corrected for the suppression of dynamic correlation with nondynamic correlation. The remaining middle-range interbond dynamic correlation is evaluated with the modified LYP functional of the bond densities. As a result, CASΠ(M)DFT potential energy curves (PECs) calculated in the relatively small triple-zeta basis closely reproduce the benchmark complete basis set PECs for the following prototype multibonded molecules: N2, CO, H2O, and C2.