Polarizability of Molecular Hydrogen

Abstract

A summation technique is used to calculate the static dipole electric polarizabilities of molecular hydrogen. The technique requires a complete set of single‐particle Hartree–Fock states. The occupied Hartree–Fock orbitals for molecular hydrogen are bound, and the complementary set of Hartree–Fock orbitals all lie in the continuum. Such a basis set permits one to evaluate the required sums by integrating over the excited states. The uncoupled Hartree–Fock model is used to calculate the zero‐order terms of the components of the polarizability tensor. The first‐order corrections to the components of the polarizability tensor are calculated using double perturbation theory. At the equilibrium internuclear separation, ${\text{R\hspace{0.17em}=\hspace{0.17em}1.4 a}}_0$ , the static parallel dipole polarizability ${\alpha }^{\Vert }$ and static perpendicular polarizability ${\alpha }^{\perp }$ are 0.941 ų and 0.728 ų, respectively, which compare favorably with the values 0.944 ų and 0.677 ų calculated by Kolos and Wolniewicz using a variation–perturbation method. The results are also in satisfactory agreement with the experimental values.