An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe-Salpeter equation calculations of molecules - CEA - Commissariat à l’énergie atomique et aux énergies alternatives
Article Dans Une Revue The Journal of Chemical Physics Année : 2022

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

Résumé

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 G0 W0 and G0 W0 -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 G0 W0 -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.
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Dates et versions

cea-04176651 , version 1 (03-08-2023)

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Caroline Mckeon, Samia Hamed, Fabien Bruneval, Jeffrey Neaton. An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe-Salpeter equation calculations of molecules. The Journal of Chemical Physics, 2022, 157, pp.074103. ⟨10.1063/5.0097582⟩. ⟨cea-04176651⟩
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