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Excitonic couplings between molecular crystal pairs by a multistate approximation
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Aragó, Juan and Troisi, Alessandro (2015) Excitonic couplings between molecular crystal pairs by a multistate approximation. The Journal of Chemical Physics, 142 (16). 164107. doi:10.1063/1.4919241 ISSN 0021-9606.
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WRAP_1275304-ch-181115-multistate_approximation_14-04-2015 (1).pdf - Accepted Version - Requires a PDF viewer. Download (1199Kb) | Preview |
Official URL: http://dx.doi.org/10.1063/1.4919241
Abstract
In this paper, we present a diabatization scheme to compute the excitonic couplings between an arbitrary number of states in molecular pairs. The method is based on an algebraic procedure to find the diabatic states with a desired property as close as possible to that of some reference states. In common with other diabatization schemes, this method captures the physics of the important short-range contributions (exchange, overlap, and charge-transfer mediated terms) but it becomes particularly suitable in presence of more than two states of interest. The method is formulated to be usable with any level of electronic structure calculations and to diabatize different types of states by selecting different molecular properties. These features make the diabatization scheme presented here especially appropriate in the context of organic crystals, where several excitons localized on the same molecular pair may be found close in energy. In this paper, the method is validated on the tetracene crystal dimer, a well characterized case where the charge transfer (CT) states are closer in energy to the Frenkel excitons (FE). The test system was studied as a function of an external electric field (to explore the effect of changing the relative energy of the CT excited state) and as a function of different intermolecular distances (to probe the strength of the coupling between FE and CT states). Additionally, we illustrate how the approximation can be used to include the environment polarization effect.
Item Type: | Journal Article | ||||||||
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Subjects: | Q Science > QC Physics | ||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Centre for Scientific Computing |
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Library of Congress Subject Headings (LCSH): | Exciton theory, Molecular crystals | ||||||||
Journal or Publication Title: | The Journal of Chemical Physics | ||||||||
Publisher: | American Institute of Physics | ||||||||
ISSN: | 0021-9606 | ||||||||
Official Date: | 28 April 2015 | ||||||||
Dates: |
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Volume: | 142 | ||||||||
Number: | 16 | ||||||||
Article Number: | 164107 | ||||||||
DOI: | 10.1063/1.4919241 | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||
Date of first compliant deposit: | 31 December 2015 | ||||||||
Date of first compliant Open Access: | 31 December 2015 | ||||||||
Funder: | Seventh Framework Programme (European Commission) (FP7), European Research Council (ERC) | ||||||||
Grant number: | FP7-PEOPLE-2012-IEF-329513 , 615834 |
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