Variational calculations on the hydrogen molecular ion

Abstract

We present high-precision non-relativistic variational calculations of bound vibrational—rotational state energies for the H⁺ ₂ and D⁺ ₂ molecular ions in each of the lowest electronic states of Σ _g , Σ _u , and Π _u symmetry. The calculations are carried out including coupling between Σ and Π states but without using the Born—Oppenheimer or any adiabatic approximation. Convergence studies are presented which indicate that the resulting energies for low-lying levels are accurate to about 10⁻¹³. Our procedure accounts naturally for the lambda-doubling of the Π _u state.