Quantum mechanical methods applied to excitation energy transfer: A comparative analysis on excitation energies and electronic couplings
- Dipartimento di Chimica e Chimica Industriale, Universita degli Studi di Pisa, Via Risorgimento 35, 56126 Pisa (Italy)
- Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica e Chimica Fisica, Universita di Parma, Parco Area delle Scienze, I-43100 Parma (Italy)
- Departamento de Ingenieria Quimica y Quimica Fisica, Universidad de Extremadura, Avda. de Elvas s/n, 06071 Badajoz (Spain)
We present a comparative study on the influence of the quantum mechanical (QM) method (including basis set) on the evaluation of transition energies, transition densities and dipoles, and excitation energy transfer (EET) electronic couplings for a series of chromophores (and the corresponding pairs) typically found in organic electro-optical devices and photosynthetic systems. On these systems we have applied five different QM levels of description of increasing accuracy (ZINDO, CIS, TD-DFT, CASSCF, and SAC-CI). In addition, we have tested the effects of a surrounding environment (either mimicking a solvent or a protein matrix) on excitation energies, transition dipoles, and electronic couplings through the polarizable continuum model (PCM) description. Overall, the results obtained suggest that the choice of the QM level of theory affects the electronic couplings much less than it affects excitation energies. We conclude that reasonable estimates can be obtained using moderate basis sets and inexpensive methods such as configuration interaction of single excitations or time-dependent density functional theory when appropriately coupled to realistic solvation models such as PCM.
- OSTI ID:
- 21106204
- Journal Information:
- Journal of Chemical Physics, Vol. 129, Issue 3; Other Information: DOI: 10.1063/1.2953716; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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