Interaction of Dark Excited States: Comparison of Computational Approaches
dc.contributor.author
dc.date.accessioned
2015-11-09T11:57:52Z
dc.date.available
2015-11-09T11:57:52Z
dc.date.issued
2015
dc.identifier.issn
1520-6106
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dc.description.abstract
A systematic theoretical study of the electronic interaction of dark excited states in a model system, formaldehyde dimer is reported. Using the fragment transition density scheme, we estimate the excitonic interaction in different configurations of the dimer. The excited state properties of the system are computed with several quantum mechanical methods. We show that the orbital interaction of the monomers rather than Coulomb interaction of their transition quadrupoles gives the major contribution to the coupling at intermolecular distances shorter than 5 Å. It is found that the exitonic interaction alters drastically by conformational changes. Benchmark couplings computed with EOM CCSD, MS-CASPT2, CASSCF, TD DFT, CIS, and INDO/S and different basis sets are provided. The evaluation of the calculations shows that the TD cam-B3LYP scheme performs best, giving good estimates for all considered structures. In contrast, the TD B3LYP scheme leads to drastically overestimated values. The data obtained using the Tamm-Dancoff approximation are similar to the TD DFT results. CASSCF and CIS calculations underestimate the coupling, indicating that dynamic electron correlation may have a large effect on the short-range coupling. The INDO/S method fails to describe the excited state interaction both at short and long distances
dc.description.sponsorship
It was a great pleasure to work with Marshall during his long-term visit to Technical University of Munich. I am very grateful for his inspiring and helpful insights into the theoretical and computational modeling of electron transfer. Financial support from MICINN (Ministry of Science and Innovation, Spain) was provided by Grant CTQ2011-26573
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application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-26573/ES/MODELIZACION QUIMICO CUANTICA DE FOTOQUIMICA Y TRANSFERENCIA ELECTRONICA: SISTEMAS GRANDES, EFECTOS COLECTIVOS Y CONTROL OPTICO/
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Reproducció digital del document publicat a: http://dx.doi.org/10.1021/jp511035p
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© Journal of Physical Chemistry B, 2015, vol. 119, núm. 24p. 7417-7421
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Articles publicats (D-Q)
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Tots els drets reservats
dc.subject
dc.title
Interaction of Dark Excited States: Comparison of Computational Approaches
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-5207