Benchmark of GW Methods for Core-Level Binding Energies

Li J, Jin Y, Rinke P, Yang W, Golze D (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Journal of Chemical Theory and Computation American Chemical Society

Book Volume: 18

Pages Range: 7570-7585

Journal Issue: 12

DOI: 10.1021/acs.jctc.2c00617

Abstract

The GW approximation has recently gained increasing attention as a viable method for the computation of deep core-level binding energies as measured by X-ray photoelectron spectroscopy. We present a comprehensive benchmark study of different GW methodologies (starting point optimized, partial and full eigenvalue-self-consistent, Hedin shift, and renormalized singles) for molecular inner-shell excitations. We demonstrate that all methods yield a unique solution and apply them to the CORE65 benchmark set and ethyl trifluoroacetate. Three GW schemes clearly outperform the other methods for absolute core-level energies with a mean absolute error of 0.3 eV with respect to experiment. These are partial eigenvalue self-consistency, in which the eigenvalues are only updated in the Green's function, single-shot GW calculations based on an optimized hybrid functional starting point, and a Hedin shift in the Green's function. While all methods reproduce the experimental relative binding energies well, the eigenvalue self-consistent schemes and the Hedin shift yield with mean absolute errors <0.2 eV the best results.

Involved external institutions

Duke University US United States (USA) (US) Aalto University Espoo FI Finland (FI) Technische Universität Dresden DE Germany (DE)

How to cite

APA:

Li, J., Jin, Y., Rinke, P., Yang, W., & Golze, D. (2022). Benchmark of GW Methods for Core-Level Binding Energies. Journal of Chemical Theory and Computation, 18(12), 7570-7585. https://doi.org/10.1021/acs.jctc.2c00617

MLA:

Li, Jiachen, et al. "Benchmark of GW Methods for Core-Level Binding Energies." Journal of Chemical Theory and Computation 18.12 (2022): 7570-7585.

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