Benchmark of Bethe-Salpeter for Triplet Excited-States
| Autor: | Ivan Duchemin, Xavier Blase, Denis Jacquemin, Aymeric Blondel |
|---|---|
| Přispěvatelé: | 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), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), 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 ) |
| Rok vydání: | 2017 |
| Předmět: |
Physics
010304 chemical physics Basis (linear algebra) 02 engineering and technology 021001 nanoscience & nanotechnology 01 natural sciences Computer Science Applications Organic molecules [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Excited state 0103 physical sciences Benchmark (computing) Quasiparticle Singlet state Physical and Theoretical Chemistry Atomic physics 0210 nano-technology Excitation Eigenvalues and eigenvectors |
| Zdroj: | Journal of Chemical Theory and Computation Journal of Chemical Theory and Computation, 2017, 13 (2), pp.767-783. ⟨10.1021/acs.jctc.6b01169⟩ Journal of Chemical Theory and Computation, American Chemical Society, 2017, 13 (2), pp.767-783. ⟨10.1021/acs.jctc.6b01169⟩ |
| ISSN: | 1549-9626 1549-9618 |
| DOI: | 10.1021/acs.jctc.6b01169 |
| Popis: | International audience; We have evaluated the accuracy of the Bethe-Salpeter singlet–triplet transition energies as well as singlet–triplet and triplet–triplet splittings for 20 organic molecules, using as reference the CC3 values determined by Thiel and co-workers with both the TZVP and aug-cc-pVTZ atomic basis sets. Our excitation energies are obtained on the basis of GW quasiparticle energy levels that are self-consistently converged with respect to the starting DFT eigenvalues. In its current form, BSE/GW is often unable to provide a balanced description of both singlet and triplet excited-states. While the singlet–singlet and triplet–triplet energy separations are obtained accurately, triplets are located too close in energy from the ground-state, by typically −0.55 eV when using standard functionals to generate the starting eigenstates. Applying the Tamm-Dancoff approximation upshifts the BSE triplet energies and allows reducing this error to ca. −0.40 eV, while using M06-HF eigenstates allows a further increase and hence a reduction of the error for triplet states, but at the cost of larger errors for the singlet excited-states. At this stage, the most accurate TD-DFT estimates therefore remain competitive for computing singlet–triplet transition energies. Indeed, with M06-2X, irrespective of the application or not of the Tamm-Dancoff approximation and of the selected atomic basis set, the deviations obtained with TD-DFT are rather small. |
| Databáze: | OpenAIRE |
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