Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 18, Issue 12, Pages 7570-7585Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.2c00617
Keywords
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Funding
- National Institute of General Medical Sciences of the National Institutes of Health [R01-GM061870]
- National Science Foundation [CHE-1900338]
- German Research Foundation [453275048]
- European Union [951786]
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This paper presents a comprehensive benchmark study on various GW methodologies for molecular inner-shell excitations. Three GW schemes, including partial eigenvalue self consistency and a Hedin shift, show superior performance in computing absolute core-level energies. While all methods reproduce relative binding energies well, the eigenvalue self-consistent schemes and the Hedin shift yield the best results with mean absolute errors below 0.2 eV.
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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