Benchmark of GW Methods for Core-Level Binding Energies

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

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2022-12-13

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en

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16
7570-7585

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Journal of Chemical Theory and Computation, Volume 18, issue 12

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.

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Funding Information: J.L. acknowledges the support from the National Institute of General Medical Sciences of the National Institutes of Health under award number R01-GM061870. W.Y. acknowledges the support from the National Science Foundation (grant no. CHE-1900338). D.G. acknowledges the Emmy Noether Programme of the German Research Foundation under project number 453275048 and P.R. the support from the European Union’s Horizon 2020 research and innovation program under grant agreement no. 951786 (the NOMAD CoE). Computing time from CSC─IT Center for Science (Finland) is gratefully acknowledged. We also thank Levi Keller for providing preliminary data for the ETFA molecule. | openaire: EC/H2020/951786/EU//NOMAD CoE

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Citation

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, vol. 18, no. 12, pp. 7570-7585 . https://doi.org/10.1021/acs.jctc.2c00617