Can GW Handle Multireference Systems?

Can GW Handle Multireference Systems?

8 Jan 2024 | Abdallah Ammar, Antoine Marie, Mauricio Rodríguez-Mayorga, Hugh G. A. Burton, and Pierre-François Loos
The study investigates the performance of the GW approximation in handling multireference molecular systems, characterized by strong electron correlation. Four scenarios are examined: the insertion of a beryllium atom into hydrogen molecules, electron detachment and attachment energies of molecules with varying multireference character, a triangular H6 cluster with spin frustration, and the dissociation of the HF molecule. The results highlight that while the GW approximation provides a quantitative description for weakly correlated systems, it struggles in strongly correlated regions, where the agreement is only qualitative. The quality of the HF reference wave function is crucial, and self-consistency does not significantly improve the results. For more strongly correlated systems, the qsGW method, which includes self-consistency over quasiparticle energies and orbitals, shows promise but still faces challenges in certain cases. Overall, the study underscores the need for careful consideration of the level of self-consistency, initial guess, and spin-symmetry breaking in the Hartree-Fock level when applying the GW approximation to multireference systems.The study investigates the performance of the GW approximation in handling multireference molecular systems, characterized by strong electron correlation. Four scenarios are examined: the insertion of a beryllium atom into hydrogen molecules, electron detachment and attachment energies of molecules with varying multireference character, a triangular H6 cluster with spin frustration, and the dissociation of the HF molecule. The results highlight that while the GW approximation provides a quantitative description for weakly correlated systems, it struggles in strongly correlated regions, where the agreement is only qualitative. The quality of the HF reference wave function is crucial, and self-consistency does not significantly improve the results. For more strongly correlated systems, the qsGW method, which includes self-consistency over quasiparticle energies and orbitals, shows promise but still faces challenges in certain cases. Overall, the study underscores the need for careful consideration of the level of self-consistency, initial guess, and spin-symmetry breaking in the Hartree-Fock level when applying the GW approximation to multireference systems.
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