Piecewise linearity in the $GW$ approximation for accurate quasiparticle energy predictions

TL;DR

This paper investigates the deviation from straight line error (DSLE) in $GW$ approximations, showing how minimizing DSLE improves agreement with experimental quasiparticle energies and proposing DSLE-minimized schemes for better accuracy.

Contribution

It identifies DSLE as a key source of discrepancy in $GW$ calculations and demonstrates how reducing DSLE through starting-point adjustments enhances predictive accuracy.

Findings

DSLE causes significant deviations in quasiparticle energy predictions.

Reducing DSLE improves agreement with experimental ionization energies.

Starting-point dependence can be exploited to minimize DSLE.

Abstract

We identify the deviation from the straight line error (DSLE) -- i.e., the spurious non-linearity of the total energy as a function of fractional particle number -- as the main source for the discrepancy between experimental vertical ionization energies and theoretical quasiparticle energies, as obtained from the $GW$ and $GW$+SOSEX approximations to many-body perturbation theory (MBPT). For self-consistent calculations, we show that $GW$ suffers from a small DSLE. Conversely, for perturbative $G_0W_0$ and $G_0W_0$+SOSEX calculations the DSLE depends on the starting point. We exploit this starting-point dependence to reduce (or completely eliminate) the DSLE. We find that the agreement with experiment increases as the DSLE reduces. DSLE-minimized schemes, thus, emerge as promising avenues for future developments in MBPT.