Assessing the performance of ab initio classical valence bond methods for hydrogen transfer reactions

Abstract

Ab initio classical valence bond theory in terms of localized orbitals has several advantages over electronic structure methods based on canonical delocalized Hartree-Fock molecular orbitals, with two key distinctions being greater applicability to inherently multiconfigurational systems (also called multireference systems or strongly correlated systems) and great interpretability in terms of covalent and ionic valence bond configurations (also called valence bond structures). This can be especially advantageous for applications to chemical reactions. However, until now only limited work tested the quantitative accuracy for the energetics of chemical reactions. The present study provides such tests and validations for a representative test set of six barrier heights corresponding to forward and reverse barriers of three hydrogen transfer reactions. In particular, we test the valence bond self-consistent-field theory (VBSCF) and three post-VBSCF methods that use VBSCF as a reference function for adding dynamic correlation, in particular valence bond configuration interaction (VBCI), breathing orbital valence bond (BOVB), and valence bond second-order perturbation theory (VBPT2). The VBSCF method itself is, as expected, not quantitatively accurate, with a mean unsigned error (MUE) for the six barrier heights of ∼17kcal/mol. But the post-VBSCF methods are found to be quite successful. Depending on the basis set, and valence bond structure selection we obtain MUEs (in kcal/mol) as low as 3.7 for VBCI, 4.5 for BOVB, and (using a bigger basis-set) 1.3 for VBPT2. These compare well, on the same data set, with 1.6 for coupled clusters with singles and doubles (CCSD) and 1.5 for multireference second order perturbation theory based on a complete active space self-consistent field reference function (MRPT2). We discuss the results in terms of the pros and cons of each of these methods.