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Title: An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe–Salpeter equation calculations of molecules

Abstract

The ab initio GW plus Bethe–Salpeter equation (GW-BSE, where G is the one particle Green's function and W is the screened Coulomb interaction) approach has emerged as a leading method for predicting excitations in both solids and molecules with a predictive power contingent upon several factors. Among these factors are the (1) generalized Kohn–Sham eigensystem used to construct the GW self-energy and to solve the BSE and (2) the efficacy and suitability of the Tamm–Dancoff approximation. Here, we present a detailed benchmark study of low-lying singlet excitations from a generalized Kohn–Sham (gKS) starting point based on an optimally tuned range-separated hybrid (OTRSH) functional. We show that the use of this gKS starting point with one-shot G0W0 and G0W0-BSE leads to the lowest mean absolute errors (MAEs) and mean signed errors (MSEs), with respect to high-accuracy reference values, demonstrated in the literature thus far for the ionization potentials of the GW100 benchmark set and for low-lying neutral excitations of Thiel’s set molecules in the gas phase, without the need for self-consistency. The MSEs and MAEs of one-shot G0W0-BSE@OTRSH excitation energies are comparable to or lower than those obtained with other functional starting points after self-consistency. Additionally, we compare these results withmore » linear-response time-dependent density functional theory (TDDFT) calculations and find GW-BSE to be superior to TDDFT when calculations are based on the same exchange-correlation functional. This work demonstrates tuned range-separated hybrids used in combination with GW and GW-BSE can greatly suppress starting point dependence for molecules, leading to accuracy similar to that for higher-order wavefunction-based theories for molecules without the need for costlier iterations to self-consistency.« less

Authors:
ORCiD logo; ; ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1882232
Grant/Contract Number:  
AC02-05CH11231; 2022-096018
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Name: Journal of Chemical Physics Journal Volume: 157 Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

McKeon, Caroline A., Hamed, Samia M., Bruneval, Fabien, and Neaton, Jeffrey B. An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe–Salpeter equation calculations of molecules. United States: N. p., 2022. Web. doi:10.1063/5.0097582.
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McKeon, Caroline A., Hamed, Samia M., Bruneval, Fabien, & Neaton, Jeffrey B. An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe–Salpeter equation calculations of molecules. United States. https://doi.org/10.1063/5.0097582
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McKeon, Caroline A., Hamed, Samia M., Bruneval, Fabien, and Neaton, Jeffrey B. Wed . "An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe–Salpeter equation calculations of molecules". United States. https://doi.org/10.1063/5.0097582.
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@article{osti_1882232,
title = {An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe–Salpeter equation calculations of molecules},
author = {McKeon, Caroline A. and Hamed, Samia M. and Bruneval, Fabien and Neaton, Jeffrey B.},
abstractNote = {The ab initio GW plus Bethe–Salpeter equation (GW-BSE, where G is the one particle Green's function and W is the screened Coulomb interaction) approach has emerged as a leading method for predicting excitations in both solids and molecules with a predictive power contingent upon several factors. Among these factors are the (1) generalized Kohn–Sham eigensystem used to construct the GW self-energy and to solve the BSE and (2) the efficacy and suitability of the Tamm–Dancoff approximation. Here, we present a detailed benchmark study of low-lying singlet excitations from a generalized Kohn–Sham (gKS) starting point based on an optimally tuned range-separated hybrid (OTRSH) functional. We show that the use of this gKS starting point with one-shot G0W0 and G0W0-BSE leads to the lowest mean absolute errors (MAEs) and mean signed errors (MSEs), with respect to high-accuracy reference values, demonstrated in the literature thus far for the ionization potentials of the GW100 benchmark set and for low-lying neutral excitations of Thiel’s set molecules in the gas phase, without the need for self-consistency. The MSEs and MAEs of one-shot G0W0-BSE@OTRSH excitation energies are comparable to or lower than those obtained with other functional starting points after self-consistency. Additionally, we compare these results with linear-response time-dependent density functional theory (TDDFT) calculations and find GW-BSE to be superior to TDDFT when calculations are based on the same exchange-correlation functional. This work demonstrates tuned range-separated hybrids used in combination with GW and GW-BSE can greatly suppress starting point dependence for molecules, leading to accuracy similar to that for higher-order wavefunction-based theories for molecules without the need for costlier iterations to self-consistency.},
doi = {10.1063/5.0097582},
journal = {Journal of Chemical Physics},
number = 7,
volume = 157,
place = {United States},
year = {Wed Aug 17 00:00:00 EDT 2022},
month = {Wed Aug 17 00:00:00 EDT 2022}
}
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