Assessing density functional theory in real-time and real-space as a tool for studying bacteriochlorophylls and the light-harvesting complex 2
| Autor: | Richard J. Cogdell, G. Matthias Ullmann, Aleksander W. Roszak, Ingo Schelter, Stephan Kümmel, Alastair T. Gardiner, Thiago Branquinho de Queiroz, Johannes M. Foerster |
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| Rok vydání: | 2019 |
| Předmět: |
Light-Harvesting Protein Complexes
General Physics and Astronomy 010402 general chemistry Space (mathematics) 01 natural sciences chemistry.chemical_compound Beijerinckiaceae 0103 physical sciences Statistical physics Physical and Theoretical Chemistry Spurious relationship Adiabatic process Bacteriochlorophylls Density Functional Theory Coupling Physics Physics::Biological Physics 010304 chemical physics 0104 chemical sciences Range (mathematics) Energy Transfer Models Chemical chemistry Density functional theory Bacteriochlorophyll Local-density approximation |
| Zdroj: | The Journal of Chemical Physics. 151:134114 |
| ISSN: | 1089-7690 0021-9606 |
| Popis: | We use real-time density functional theory on a real-space grid to calculate electronic excitations of bacteriochlorophyll chromophores of the light-harvesting complex 2 (LH2). Comparison with Gaussian basis set calculations allows us to assess the numerical trust range for computing electron dynamics in coupled chromophores with both types of techniques. Tuned range-separated hybrid calculations for one bacteriochlorophyll as well as two coupled ones are used as a reference against which we compare results from the adiabatic time-dependent local density approximation (TDLDA). The tuned range-separated hybrid calculations lead to a qualitatively correct description of the electronic excitations and couplings. They allow us to identify spurious charge-transfer excitations that are obtained with the TDLDA. When we take into account the environment that the LH2 protein complex forms for the bacteriochlorophylls, we find that it substantially shifts the energy of the spurious charge-transfer excitations, restoring a qualitatively correct electronic coupling of the dominant excitations also for TDLDA. |
| Databáze: | OpenAIRE |
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