GW plus cumulant approach for predicting core-level shake-up satellites in large molecules

TL;DR

This paper extends the $GW+C$ approach to better predict core-level shake-up satellites in large molecules, achieving improved accuracy and efficiency in modeling X-ray photoemission spectra.

Contribution

The authors develop an $GW+C$ method tailored for molecular 1s excitations, with an efficient implementation and validation for large molecules, improving satellite feature predictions.

Findings

Accurately predicts satellite features within 0.5 eV of experiments.

Highlights importance of basis set convergence and diffuse functions.

Provides insights into satellite features in acenes from benzene to pentacene.

Abstract

Recently, the $GW$ approach has emerged as a valuable tool for computing deep core-level binding energies as measured in X-ray photoemission spectroscopy. However, $GW$ fails to accurately predict shake-up satellite features, which arise from charge-neutral excitations accompanying the ionization. In this work, we extend the $GW$ plus cumulant ($GW+C$) approach to molecular 1s excitations, deriving conditions under which $GW+C$ can be reliably applied to shake-up processes. We present an efficient implementation with $O(N^4)$ scaling with respect to the system size $N$, within an all-electron framework based on numeric atom-centered orbitals. We demonstrate that decoupling the core and valence spaces is crucial when using localized basis functions. Additionally, we meticulously validate the basis set convergence of the satellite spectrum for 65 spectral functions and identify the importance of diffuse augmenting functions. To assess the accuracy, we apply our $GW+C$ scheme to $\pi$-conjugated molecules containing up to 40 atoms, predicting dominant satellite features within 0.5~eV of experimental values. For the acene series, from benzene to pentacene, we demonstrate how $GW+C$ provides critical insights into the interpretation of experimentally observed satellite features.