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Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2024

Fully dynamic G3W2 self-energy for finite systems: Formulas and benchmark

Résumé

Over the years, Hedin's GW self-energy has been proven to be a rather accurate and simple approximation to evaluate electronic quasiparticle energies in solids and in molecules. Attempts to improve over the simple GW approximation, the so-called vertex corrections, have been constantly proposed in the literature. Here, we derive, analyze, and benchmark the complete second-order term in the screened Coulomb interaction W for finite systems. This self-energy named G3W2 contains all the possible time orderings that combine 3 Green's functions G and 2 dynamic W. We present the analytic formula and its imaginary frequency counterpart, the latter allowing us to treat larger molecules. The accuracy of the G3W2 self-energy is evaluated on well-established benchmarks (GW100, Acceptor 24 and Core 65) for valence and core quasiparticle energies. Its link with the simpler static approximation, named SOSEX for static screened second-order exchange, is analyzed, which leads us to propose a more consistent approximation named 2SOSEX. Notably, both our formula for the G3W2 expression and our numerical results differ from the expression published in a recent study by Wang et. al. [J. Chem. Theory Comput. 17, 5140 (2021)] In the end, we find that neither the G3W2 self-energy nor any of the investigated approximations to it improve over one-shot G$_0$W$_0$ with a good starting point. Only quasi-particle self-consistent GW HOMO energies are slightly improved by addition of the G3W2 self-energy correction. We show that this is due to the self-consistent update of the screened Coulomb interaction leading to an overall sign change of the vertex correction to the frontier quasiparticle energies.
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Dates et versions

cea-04604065 , version 1 (06-06-2024)

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Fabien Bruneval, Arno Förster. Fully dynamic G3W2 self-energy for finite systems: Formulas and benchmark. Journal of Chemical Theory and Computation, 2024, 20, pp.3218-3230. ⟨10.1021/acs.jctc.4c00090⟩. ⟨cea-04604065⟩
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