Spin-symmetry adaptation to the Monte Carlo correction configuration interaction wave functions.

Abstract

We propose a method to adapt the spin-symmetry to the Monte Carlo correction configuration interaction (MC3I) wave function which is expanded by the selected Slater determinants (SDs). The spin-symmetry of the MC3I wave function is usually broken because the Monte Carlo method is used to select the SDs, and this problem becomes worse as the electron correlation becomes stronger. In the present method, the S^2 operator is applied to the set of the SDs in the MC3I wave function iteratively until the set becomes closed under S^2. The spin-symmetry adapted MC3I wave functions are calculated by diagonalization of the Hamiltonian matrix which is spanned by the converged set of SDs. The present method is tested by the application to the excited states of C2 in the bond dissociation region and the 100 lowest states of [Fe2S2(SCH3)4]3-. The deviations of S (total spin angular momentum) of some states were too large to assign the electronic states in the original MC3I calculations, while all states have the correct S after spin-symmetry adaptation and become comparable with the full configuration interaction and density matrix renormalization group results. With the present spin-symmetry adaptation, the MC3I method becomes applicable to strong electron correlation systems.