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Title: A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules

Abstract

The predictive power of the ab initio Bethe-Salpeter equation (BSE) approach, rigorously based on many-body Green’s function theory but incorporating information from density functional theory, has already been demonstrated for the optical gaps and spectra of solid-state systems. Interest in photoactive hybrid organic/inorganic systems has recently increased and so has the use of the BSE for computing neutral excitations of organic molecules. However, no systematic benchmarks of the BSE for neutral electronic excitations of organic molecules exist. Here, we study the performance of the BSE for the 28 small molecules in Thiel’s widely used time-dependent density functional theory benchmark set [Schreiber et al., J. Chem. Phys. 128, 134110 (2008)]. We observe that the BSE produces results that depend critically on the mean-field starting point employed in the perturbative approach. We find that this starting point dependence is mainly introduced through the quasiparticle energies obtained at the intermediate GW step and that with a judicious choice of starting mean-field, singlet excitation energies obtained from BSE are in excellent quantitative agreement with higher-level wavefunction methods. The quality of the triplet excitations is slightly less satisfactory.

Authors:
 [1];  [2];  [2];  [3];  [2];  [2];  [2];  [3];  [2];  [2]
  1. CEA, DEN, Service de Recherches de Métallurgie Physique, F-91191 Gif-sur-Yvette (France)
  2. (United States)
  3. Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22489543
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 24; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 97 MATHEMATICAL METHODS AND COMPUTING; BETHE-SALPETER EQUATION; DENSITY FUNCTIONAL METHOD; EXCITATION; MANY-BODY PROBLEM; MEAN-FIELD THEORY; MOLECULES; SOLIDS; SPECTRA; TIME DEPENDENCE

Citation Formats

Bruneval, Fabien, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Department of Physics, University of California, Berkeley, California 94720, Hamed, Samia M., Department of Physics, University of California, Berkeley, California 94720, Department of Chemistry, University of California, Berkeley, California 94720, Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720, Neaton, Jeffrey B., Department of Physics, University of California, Berkeley, California 94720, and Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720. A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules. United States: N. p., 2015. Web. doi:10.1063/1.4922489.
Bruneval, Fabien, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Department of Physics, University of California, Berkeley, California 94720, Hamed, Samia M., Department of Physics, University of California, Berkeley, California 94720, Department of Chemistry, University of California, Berkeley, California 94720, Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720, Neaton, Jeffrey B., Department of Physics, University of California, Berkeley, California 94720, & Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720. A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules. United States. doi:10.1063/1.4922489.
Bruneval, Fabien, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Department of Physics, University of California, Berkeley, California 94720, Hamed, Samia M., Department of Physics, University of California, Berkeley, California 94720, Department of Chemistry, University of California, Berkeley, California 94720, Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720, Neaton, Jeffrey B., Department of Physics, University of California, Berkeley, California 94720, and Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720. Sun . "A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules". United States. doi:10.1063/1.4922489.
@article{osti_22489543,
title = {A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules},
author = {Bruneval, Fabien and Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Department of Physics, University of California, Berkeley, California 94720 and Hamed, Samia M. and Department of Physics, University of California, Berkeley, California 94720 and Department of Chemistry, University of California, Berkeley, California 94720 and Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720 and Neaton, Jeffrey B. and Department of Physics, University of California, Berkeley, California 94720 and Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720},
abstractNote = {The predictive power of the ab initio Bethe-Salpeter equation (BSE) approach, rigorously based on many-body Green’s function theory but incorporating information from density functional theory, has already been demonstrated for the optical gaps and spectra of solid-state systems. Interest in photoactive hybrid organic/inorganic systems has recently increased and so has the use of the BSE for computing neutral excitations of organic molecules. However, no systematic benchmarks of the BSE for neutral electronic excitations of organic molecules exist. Here, we study the performance of the BSE for the 28 small molecules in Thiel’s widely used time-dependent density functional theory benchmark set [Schreiber et al., J. Chem. Phys. 128, 134110 (2008)]. We observe that the BSE produces results that depend critically on the mean-field starting point employed in the perturbative approach. We find that this starting point dependence is mainly introduced through the quasiparticle energies obtained at the intermediate GW step and that with a judicious choice of starting mean-field, singlet excitation energies obtained from BSE are in excellent quantitative agreement with higher-level wavefunction methods. The quality of the triplet excitations is slightly less satisfactory.},
doi = {10.1063/1.4922489},
journal = {Journal of Chemical Physics},
number = 24,
volume = 142,
place = {United States},
year = {Sun Jun 28 00:00:00 EDT 2015},
month = {Sun Jun 28 00:00:00 EDT 2015}
}