Exact two-component Hamiltonians for relativistic quantum chemistry: Two-electron picture-change corrections made simple

TL;DR

This paper introduces two efficient matrix-algebraic methods, amfX2C and e(xtended)amfX2C, for accurately correcting two-electron picture-change effects in relativistic quantum chemistry within an exact two-component Hamiltonian framework.

Contribution

The paper presents novel, computationally efficient PCE correction models that are adaptable to mean-field theories, simplifying relativistic quantum chemical calculations.

Findings

Achieved ~10^-5 Hartree accuracy in spinor energies compared to four-component data.

Demonstrated high accuracy in molecular property calculations, including contact densities and ionization energies.

Validated models across various molecules, showing excellent agreement with reference data.

Abstract

Based on self-consistent field (SCF) atomic mean-field (amf) quantities, we present two simple, yet computationally efficient and numerically accurate matrix-algebraic approaches to correct both scalar-relativistic \textit{and} spin-orbit two-electron picture-change effects (PCE) arising within an exact two-component (X2C) Hamiltonian framework. Both approaches, dubbed amfX2C and e(xtended)amfX2C, allow us to uniquely tailor PCE corrections to mean-field models, $viz.$ Hartree-Fock or Kohn-Sham DFT, in the latter case also avoiding the need of a point-wise calculation of exchange-correlation PCE corrections. We assess the numerical performance of these PCE correction models on spinor energies of group-18 (closed-shell) and group-16 (open-shell) diatomic molecules, achieving a consistent $\approx\!10^{-5}$ Hartree accuracy compared to reference four-component data. Additional tests include SCF calculations of molecular properties such as absolute contact density and contact density shifts in copernicium fluoride compounds (CnF$_{n}$, n=2,4,6), as well as equation-of-motion coupled cluster calculations of X-ray core ionization energies of $5d$ and $6d$-containing molecules, where we observe an excellent agreement with reference data. To conclude, we are confident that our (e)amfX2C PCE correction models constitute a fundamental milestone towards a universal and reliable relativistic two-component quantum chemical approach, maintaining the accuracy of the parent four-component one at a fraction of its computational cost.