1. Benchmarking the Bethe-Salpeter Formalism on a Standard Organic Molecular Set
- Author
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Ivan Duchemin, Denis Jacquemin, Xavier Blase, Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratory of Atomistic Simulation (LSIM ), Modélisation et Exploration des Matériaux (MEM), Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Théorie de la Matière Condensée (NEEL - TMC), Institut Néel (NEEL), Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS), ANR-12-BS04-0001,PANELS,Simulations ab initio innovantes pour le photovoltaïque(2012), European Project: 278845,EC:FP7:ERC,ERC-2011-StG_20101014,MARCHES(2012), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), Théorie de la Matière Condensée (TMC), and Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Joseph Fourier - Grenoble 1 (UJF)
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Theoretical computer science ,Excitation-Energies ,Computer science ,Electronically Excited-States ,01 natural sciences ,Article ,Density-Functional Theory ,Quantum mechanics ,0103 physical sciences ,Greens-Function Theory ,Physical and Theoretical Chemistry ,010306 general physics ,[PHYS]Physics [physics] ,010304 chemical physics ,Ab-Initio Calculation ,Chromophores ,Redshift ,Computer Science Applications ,Hybrid functional ,Formalism (philosophy of mathematics) ,Coupled cluster ,Coupled-Cluster ,Reference values ,Quasiparticle ,Density functional theory ,Spectroscopic Properties ,TD-DFT ,Excitation ,Optical-Absorption - Abstract
International audience; We perform benchmark calculations of the Bethe Salpeter vertical excitation energies for the set of 28 molecules constituting the well-known Thiel's set, complemented by a series of small molecules representative of the dye chemistry field. We show that Bethe Salpeter calculations based on a molecular orbital energy spectrum obtained with non-self-consistent G(0)W(0) calculations starting from semilocal DFT functionals dramatically underestimate the transition energies. Starting from the popular PBEO hybrid functional significantly improves the results even though this leads to an average -0.59 eV redshift compared to reference calculations for Thiel's set. It is shown, however, that a simple self-consistent scheme at the GW level, with an update of the quasiparticle energies, not only leads to a much better agreement with reference values, but also significantly reduces the impact of the starting DFT functional. On average, the Bethe Salpeter scheme based on self-consistent GW calculations comes close to the best timedependent DFT calculations with the PBEO functional with a 0.98 correlation coefficient and a 0.18 (0.25) eV mean absolute deviation compared to TD-PBEO (theoretical best estimates) with a tendency to be red-shifted. We also observe that TD-DFT and the standard adiabatic Bethe Salpeter implementation may differ significantly for states implying a large multiple excitation character.
- Published
- 2015
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