The Dirac equation for ${{\mathrm{H}}_2}^{+}$ is solved numerically by expansion in a basis set of two-center exponential functions, using different kinetic balance schemes. Very high precision (27 to 32 digits) is achieved, either with the dual kinetic balance, which provides the fastest convergence, or without imposing any kinetic balance condition. An application to heavy molecular ions is also illustrated. The 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.

• Received 13 February 2023
• Accepted 14 April 2023

DOI:https://doi.org/10.1103/PhysRevA.107.042817