All-Electron Relativistic Fully Self-Consistent $GW$ Study of Heteronuclear Actinide-Containing Diatomics

Abstract

The fully self-consistent $GW$ (sc$GW$) approximation provides a Green's-function approach that is starting-point independent and offers a favorable cost-to-accuracy balance compared to high-level wavefunction methods. Here, we present an all-electron sc$GW$ study of uranium-containing diatomics (UC, UN, UO, and UF), incorporating relativistic effects through the exact two-component (X2C) formalism. We evaluate adiabatic ionization energies as well as electron-attachment and detachment energetics (AEA and VDE), together with equilibrium structures and harmonic vibrational frequencies, and we assess their sensitivity to basis-set choice and relativistic treatment. We find that sc$GW$ yields ionization energies and vibrational properties in very good agreement with experiment and high-accuracy theoretical estimates. For AEA and VDE, diffuse basis sets are essential for convergence. UF is a particularly challenging case for scalar relativistic methods because its electron-attachment and vertical detachment energies are strongly affected by spin--orbit coupling, highlighting the need for a variational two-component treatment. These results establish all-electron X2C-sc$GW$ as a practical route for accurate actinide-molecule energetics and spectroscopy and motivate future applications to larger uranium-containing systems.