One-Electron Energies from the Two-Component GW Method.

Area of Science:

• Quantum chemistry
• Computational physics
• Electronic structure theory

Background:

• The G0W0 method is a standard tool for calculating electronic properties of molecules.
• Accurate calculations of electronic properties require accounting for relativistic effects like spin-orbit coupling.
• Previous implementations of G0W0 were limited to non-relativistic calculations.

Purpose of the Study:

• To develop and implement a two-component G0W0 method for closed-shell systems.
• To incorporate spin-orbit effects into G0W0 calculations for isolated molecular systems.
• To assess the accuracy of the new method for ionization energies and core-level binding energies.

Main Methods:

• Extension of the one-component G0W0 method to a two-component formalism.
• Utilizing localized basis functions within the TURBOMOLE software.
• Application to atomic and diatomic systems, including mercury, zinc, and ZnF2.

Main Results:

• The two-component G0W0 method accurately accounts for spin-orbit effects on one-electron energies.
• Calculated first ionization energies showed changes up to 0.7 eV due to spin-orbit coupling.
• An economic extrapolation scheme provided results comparable to the full two-component calculation.
• High accuracy was achieved for core-level binding energies.

Conclusions:

• The developed two-component G0W0 method is a reliable tool for including spin-orbit effects in electronic structure calculations.
• The method provides accurate predictions for ionization potentials and core-level binding energies.
• The computational cost can be managed using extrapolation schemes without significant loss of accuracy.