Assessing the $G_0W_0\Gamma^{(1)}_0$ approach: Beyond $G_0W_0$ with Hedin's full second-order self-energy contribution

TL;DR

This paper introduces and benchmarks a new self-energy method that extends the $GW$ approximation by including the full second-order self-energy, improving the accuracy of quasiparticle energy calculations for molecules.

Contribution

The paper develops a $G_0W_0 ext{}\Gamma^{(1)}_0$ approach incorporating the full second-order self-energy, providing a more accurate vertex correction beyond standard $GW$ methods.

Findings

$G_0W_0 ext{ }\Gamma^{(1)}_0$ outperforms $G_0W_0$ in predicting ionization potentials and electron affinities.

Implementation scales better than $O(N^5)$ for small to medium molecules.

Static FSOS-$W$ significantly underestimates quasiparticle energies.

Abstract

We present and benchmark a self-energy approach for quasiparticle energy calculations that goes beyond Hedin's $GW$ approximation by adding the full second-order self-energy (FSOS-$W$) contribution. The FSOS-$W$ diagram involves two screened Coulomb interaction ($W$) lines and adding the FSOS-$W$ to the $GW$ self-energy can be interpreted as first-order vertex correction to $GW$ ($GW\Gamma^{(1)}$). Our FSOS-$W$ implementation is based on the resolution-of-identity technique and exhibits better than $O(N^5)$ scaling with system size for small to medium-sized molecules. We then present one-shot $GW\Gamma^{(1)}$ ($G_0W_0\Gamma^{(1)}_0$) benchmarks for the $GW$100 test set and a set of 24 acceptor molecules. For semilocal or hybrid density functional theory starting points, $G_0W_0\Gamma^{(1)}_0$ systematically outperforms $G_0W_0$ for the first vertical ionization potentials (vIPs) and electron affinities (vEAs) of both test sets. Finally, we demonstrate that a static FSOS-$W$ self-energy significantly underestimates the quasiparticle energies.