TY - JOUR
T1 - Benchmark of GW Methods for Core-Level Binding Energies
AU - Li, Jiachen
AU - Jin, Ye
AU - Rinke, Patrick
AU - Yang, Weitao
AU - Golze, Dorothea
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/12/13
Y1 - 2022/12/13
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85141802167&partnerID=8YFLogxK
U2 - 10.1021/acs.jctc.2c00617
DO - 10.1021/acs.jctc.2c00617
M3 - Article
C2 - 36322136
AN - SCOPUS:85141802167
SN - 1549-9618
VL - 18
SP - 7570
EP - 7585
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 12
ER -