Different forms of the zeroth-order Hamiltonian in second-order perturbation theory with a complete active space self-consistent field reference function

Summary

A new one-particle zeroth-order Hamiltonian is proposed for perturbation theory with a complete active space self-consistent field (CASSCF) reference function. With the new partitioning of the Hamiltonian, reference functions dominated by a closed-shell configuration, on one hand, and an open-shell configuration, on the other hand, are treated in similar and balanced ways. This leads to a better description of excitation energies and dissociation energies. The new zeroth-order Hamiltonian has been tested on CH₂, SiH₂, NH₂, CH₃, N₂, NO, and O₂, for which full configuration interaction (FCI) results are available. Further, excitation energies and dissociation energies for the N₂ molecule have been compared to corresponding multireference (MR) CI results. Finally, the dissociation energies for a large number of benchmark molecules containing first-row atoms (the “G1” test) have been compared to experimental data. The computed excitation energies compare very well with the corresponding FCI and MRCI values. In most cases the errors are well below 1 kcal/mol. The dissociation energies, on the other hand, are in general improved in the new treatment but have a tendency to be overestimated when compared to other more accurate methods.