All-Electron BSE@ GW Method for K-Edge Core Electron Excitation Energies

Yao Y, Golze D, Rinke P, Blum V, Kanai Y (2022)

Publication Type: Journal article

Publication year: 2022

Journal

Journal of Chemical Theory and Computation American Chemical Society

Book Volume: 18

Pages Range: 1569-1583

Journal Issue: 3

DOI: 10.1021/acs.jctc.1c01180

Abstract

We present an accurate computational approach to calculate absolute K-edge core electron excitation energies as measured by X-ray absorption spectroscopy. Our approach employs an all-electron Bethe-Salpeter equation (BSE) formalism based on GW quasiparticle energies (BSE@GW) using numeric atom-centered orbitals (NAOs). The BSE@GW method has become an increasingly popular method for the computation of neutral valence excitation energies of molecules. However, it was so far not applied to molecular K-edge excitation energies. We discuss the influence of different numerical approximations on the BSE@GW calculation and employ in our final setup (i) exact numeric algorithms for the frequency integration of the GW self-energy, (ii) G0W0and BSE starting points with ∼50% of exact exchange, (iii) the Tamm-Dancoff approximation and (iv) relativistic corrections. We study the basis set dependence and convergence with common Gaussian-type orbital and NAO basis sets. We identify the importance of additional spatially confined basis functions as well as of diffuse augmenting basis functions. The accuracy of our BSE@GW method is assessed for a benchmark set of small organic molecules, previously used for benchmarking the equation-of-motion coupled cluster method [Peng et al., J. Chem. Theory Comput., 2015, 11, 4146], as well as the medium-sized dibenzothiophene (DBT) molecule. Our BSE@GW results for absolute excitation energies are in excellent agreement with the experiment, with a mean average error of only 0.63 eV for the benchmark set and with errors <1 eV for the DBT molecule.

Involved external institutions

University of North Carolina at Chapel Hill US United States (USA) (US) Technische Universität Dresden DE Germany (DE) Aalto University Espoo FI Finland (FI) Duke University US United States (USA) (US)

How to cite

APA:

Yao, Y., Golze, D., Rinke, P., Blum, V., & Kanai, Y. (2022). All-Electron BSE@ GW Method for K-Edge Core Electron Excitation Energies. Journal of Chemical Theory and Computation, 18(3), 1569-1583. https://doi.org/10.1021/acs.jctc.1c01180

MLA:

Yao, Yi, et al. "All-Electron BSE@ GW Method for K-Edge Core Electron Excitation Energies." Journal of Chemical Theory and Computation 18.3 (2022): 1569-1583.

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