Which Ab Initio Wave Function Methods Are Adequate for Quantitative Calculations of the Energies of Biradicals? The Performance of Coupled-Cluster and Multi-Reference Methods Along a Single-Bond Dissociation Coordinate.

Abstract

We examine the accuracy of single-reference and multireference correlated wave function methods for predicting accurate energies and potential energy curves of biradicals. The biradicals considered are intermediate species along the bond dissociation coordinates for breaking the F-F bond in F2, the O-O bond in H2O2, and the C-C bond in CH3CH3. We apply a host of single-reference and multireference approximations in a consistent way to the same cases to provide a better assessment of their relative accuracies than was previously possible. The most accurate method studied is coupled cluster theory with all connected excitations through quadruples, CCSDTQ. Without explicit quadruple excitations, the most accurate potential energy curves are obtained by the single-reference RCCSDt method, followed, in order of decreasing accuracy, by UCCSDT, RCCSDT, UCCSDt, seven multireference methods, including perturbation theory, configuration interaction, and coupled-cluster methods (with MRCI+Q being the best and Mk-MR-CCSD the least accurate), four CCSD(T) methods, and then CCSD.