Full Wave Function Optimization with Quantum Monte Carlo-A Study of the Dissociation Energies of ZnO, FeO, FeH, and...

The dissociation energies of four transition-metal dimers are determined using diffusion Monte Carlo. The Jastrow, configuration interaction, and molecular orbital parameters of the wave function are both partially and fully optimized with respect to the variational energy. The pivotal role is thereby ascribable to the optimization of the molecular orbital parameters of a complete active space wave function in the presence of a Jastrow correlation function. Excellent results are obtained for ZnO, FeO, FeH, and CrS. In addition, potential energy curves are computed for the first three compounds at the multireference diffusion Monte Carlo (MR-DMC) level, from which spectroscopic constants such as the equilibrium bond distance, the harmonic frequency, and the anharmonicity are extracted. All of these quantities agree well with the experiment. Furthermore, it is shown for CrS that a restricted active space calculation can yield improved initial orbitals by including single and double excitations from the original active space into a set of virtual orbitals. We demonstrated in this study that the fixed-node error in DMC can be systematically reduced for multireference systems by orbital optimization in compact active spaces. Although DMC calculations with a large number of determinants are possible and very accurate, our results demonstrate that compact wave functions may be sufficient in order to obtain accurate nodal surfaces, which determine the accuracy of DMC, even in the case of transition-metal compounds.