Investigation of Multiconfigurational Short-Range Density Functional Theory for Electronic Excitations in Organic Molecules
| Autor: | Hans Jørgen Aa. Jensen, Erik D. Hedegård, Mickaël Hubert |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2016 |
| Předmět: |
Chemical substance
010304 chemical physics Computer science Nanotechnology 010402 general chemistry 01 natural sciences 0104 chemical sciences Computer Science Applications Organic molecules Set (abstract data type) Range (mathematics) Character (mathematics) 0103 physical sciences Benchmark (computing) Molecule Density functional theory Statistical physics Physical and Theoretical Chemistry |
| Zdroj: | Hubert, M, Hedegård, E D & Jensen, H J A 2016, ' Investigation of Multiconfigurational Short-Range Density Functional Theory for Electronic Excitations in Organic Molecules ', Journal of Chemical Theory and Computation, vol. 12, no. 5, pp. 2203-2213 . https://doi.org/10.1021/acs.jctc.5b01141 |
| DOI: | 10.1021/acs.jctc.5b01141 |
| Popis: | Computational methods that can accurately and effectively predict all types of electronic excitations for any molecular system are missing in the toolbox of the computational chemist. Although various Kohn–Sham density-functional methods (KS-DFT) fulfill this aim in some cases, they become inadequate when the molecule has near-degeneracies and/or low-lying double-excited states. To address these issues we have recently proposed multiconfiguration short-range density-functional theory—MC-srDFT—as a new tool in the toolbox. While initial applications for systems with multireference character and double excitations have been promising, it is nevertheless important that the accuracy of MC-srDFT is at least comparable to the best KS-DFT methods also for organic molecules that are typically of single-reference character. In this paper we therefore systematically investigate the performance of MC-srDFT for a selected benchmark set of electronic excitations of organic molecules, covering the most common types of organic chromophores. This investigation confirms the expectation that the MC-srDFT method is accurate for a broad range of excitations and comparable to accurate wave function methods such as CASPT2, NEVPT2, and the coupled cluster based CC2 and CC3. Computational methods that can accurately and effectively predict all types of electronic excitations for any molecular system are missing in the toolbox of the computational chemist. Although various Kohn-Sham density-functional methods (KS-DFT) fulfill this aim in some cases, they become inadequate when the molecule has near-degeneracies and/or low-lying double-excited states. To address these issues we have recently proposed multiconfiguration short-range density-functional theory-MC-srDFT-as a new tool in the toolbox. While initial applications for systems with multireference character and double excitations have been promising, it is nevertheless important that the accuracy of MC-srDFT is at least comparable to the best KS-DFT methods also for organic molecules that are typically of single-reference character. In this paper we therefore systematically investigate the performance of MC-srDFT for a selected benchmark set of electronic excitations of organic molecules, covering the most common types of organic chromophores. This investigation confirms the expectation that the MC-srDFT method is accurate for a broad range of excitations and comparable to accurate wave function methods such as CASPT2, NEVPT2, and the coupled cluster based CC2 and CC3. |
| Databáze: | OpenAIRE |
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