Explicitly correlated Gaussian functions with shifted-center and projection techniques in pre-Born-Oppenheimer calculations.

Abstract

Numerical projection methods are elaborated for the calculation of eigenstates of the non-relativistic many-particle Coulomb Hamiltonian with selected rotational and parity quantum numbers employing shifted explicitly correlated Gaussian functions, which are, in general, not eigenfunctions of the total angular momentum and parity operators. The increased computational cost of numerically projecting the basis functions onto the irreducible representations of the three dimensional rotation-inversion group is the price to pay for the increased flexibility of the basis functions. This increased flexibility allowed us to achieve a substantial improvement for the variational upper bound to the Pauli-allowed ground-state energy of the molecular ion treated as an explicit five-particle system. We compare our pre-Born-Oppenheimer result obtained for this molecular ion with rotational-vibrational calculations carried out on a potential energy surface.