Vertex corrections to the polarizability do not improve the GW approximation for the ionization potential of molecules

TL;DR

This study examines whether including vertex corrections in the polarizability improves the accuracy of GW calculations for molecular ionization potentials, finding that it does not and can worsen predictions.

Contribution

The paper demonstrates that vertex corrections in the polarizability do not enhance GW ionization potential predictions and may lead to increased errors.

Findings

Vertex corrections in polarizability do not improve GW ionization potentials.

Using vertex-corrected polarizability increases mean absolute error from 0.3 eV to 0.5 eV.

Eigenvalue self-consistency worsens predictions with vertex corrections.

Abstract

The $GW$ approximation is based on the neglect of vertex corrections, which appear in the exact self-energy and the exact polarizability. Here, we investigate the importance of vertex corrections in the polarizability only. We calculate the polarizability with equation-of-motion coupled-cluster theory with single and double excitations (EOM-CCSD), which rigorously includes a large class of diagrammatically-defined vertex corrections beyond the random phase approximation (RPA). As is well-known, the frequency-dependent polarizability predicted by EOM-CCSD is quite different and generally more accurate than that predicted by the RPA. We evaluate the effect of these vertex corrections on a test set of 20 atoms and molecules. When using a Hartree-Fock reference, ionization potentials predicted by the $GW$ approximation with the RPA polarizability are typically overestimated with a mean absolute error of 0.3 eV. However, those predicted with a vertex-corrected polarizability are typically underestimated with an increased mean absolute error of 0.5 eV. This result suggests that vertex corrections in the self-energy cannot be neglected, at least for molecules. We also assess the behavior of eigenvalue self-consistency in vertex-corrected $GW$ calculations, finding a further worsening of the predicted ionization potentials.