High-precision solution of the Dirac Equation for the hydrogen molecular ion using a basis-set expansion

Abstract

The Dirac equation for H$_2^+$ is solved numerically by expansion in a basis set of two-center exponential functions, using different kinetic balance schemes. Very high precision (27-32 digits) is achieved, either with the dual kinetic balance, which provides the fastest convergence, or without imposing any kinetic balance condition. Application to heavy molecular ions is also illustrated. Calculation of relativistic sum rules shows that this method gives an accurate representation of the complete Dirac spectrum, making it a promising tool for calculations of QED corrections in molecular systems.