Symmetry-Projected Nuclear-Electronic Hartree-Fock: Eliminating Rotational Energy Contamination.

Abstract

We present a symmetry projection technique for enforcing rotational and parity symmetries in nuclear-electronic Hartree-Fock wave functions, which treat electrons and nuclei on equal footing. The molecular Hamiltonian obeys rotational and parity inversion symmetries, which are, however, broken by expanding in Gaussian basis sets that are fixed in space. We generate a trial wave function with the correct symmetry properties by projecting the wave function onto representations of the three-dimensional rotation group, i.e., the special orthogonal group in three dimensions SO(3). As a consequence, the wave function becomes an eigenfunction of the angular momentum operator which (i) eliminates the contamination of the ground-state wave function by highly excited rotational states arising from the broken rotational symmetry and (ii) enables the targeting of specific rotational states of the molecule. We demonstrate the efficiency of the symmetry projection technique by calculating the energies of the low-lying rotational states of the H2 and H3+ molecules.