Singlet-triplet gaps in diradicals obtained with diffusion quantum Monte Carlo using a Slater-Jastrow trial wavefunction with a minimum number of determinants.

Abstract

Diradicals are essential species in a wide range of chemical processes, whereas the computational study of their electronic structure often remains a challenge due to near-degeneracy of the frontier molecular orbitals. The fixed-node diffusion quantum Monte Carlo (FN-DMC) method is employed to calculate adiabatic energy gaps of some typical diradicals with the Slater-Jastrow trial wavefunction. The antisymmetrized part of the trial wavefunction is taken to be a linear combination of a minimum number of determinants using RB3LYP orbitals from the closed-shell singlet state or ROB3LYP orbitals from the triplet state. Our results show that using the two-determinant-Jastrow trial wavefunction is necessary to achieve reliable energy differences between closed-shell singlet states. The energy of the triplet state with MS = 1 is calculated to be lower than that with MS = 0 with FN-DMC even using trial wavefunctions with spin-pure states as their antisymmetrized parts and this difference is reduced with better orbitals. This indicates that the fixed-node error is smaller for the triplet state with MS = 1. Adiabatic energy gaps obtained from the present FN-DMC calculations are in reasonable agreement with available experimental values. Compared with results of the high level EOM-SF-CC method, energy gaps of FN-DMC with RB3LYP orbitals are slightly better than those using ROB3LYP orbitals and results of EOM-SF-CCSD. The present FN-DMC calculations using the simplest ansatz for the trial wavefunction can achieve reasonable results for these diradicals and they can readily be applied to large diradicals.