Exploring the Statically Screened $G3W2$ Correction to the $GW$ Self-Energy: Charged Excitations and Total Energies of Finite Systems

Abstract

Electron correlation in finite and extended systems is often described in an effective single-particle framework within the $GW$ approximation. Here, we use the statically screened second-order exchange contribution to the self-energy ($G3W2$) to calculate a perturbative correction to the $GW$ self-energy. We use this correction to calculate total correlation energies of atoms, relative energies, as well as charged excitations of a wide range of molecular systems. We show that the second-order correction improves correlation energies with respect to the RPA and also improves relative energies for many, but not all considered systems. While the full $G3W2$ contribution does not give consistent improvements over $GW$, taking the average of $GW$ and $GW+G3W2$ generally gives excellent results. Improvements over quasiparticle self-consistent $GW$, which we show to give very accurate charged excitations in small and medium molecules by itself, are only minor. $G_0{W}_0$ quasiparticle energies evaluated with eigenvalue and orbitals from range-separated hybrids, however, are tremendously improved upon: The second-order corrected $G_0{W}_0$ outperforms all existing $GW$ methods for the systems considered herein and also does not come with substantially increased computational cost compared to $G_0{W}_0$ for systems with up to 100 atoms.

Revised version as accepted by Physical review B (Phys. Rev. B 2022, 105, 125121, 10.1103/PhysRevB.105.125121) Compared to our first submission, a programming mistake in our first implementation has been corrected leading to different (better) results

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