Estimation of electronic coupling for singlet excitation energy transfer
dc.contributor.author
dc.date.accessioned
2016-02-08T13:43:51Z
dc.date.available
2016-02-08T13:43:51Z
dc.date.issued
2014
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1932-7447
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dc.description.abstract
Electronic coupling is a key parameter that controls the efficiency of excitation energy transfer (EET) and exciton delocalization. A new approach to estimate electronic coupling is introduced. Within a two-state model, the EET coupling V of two chromophores is expressed via the vertical excitation energies (Ei and Ej), transition dipole moments (Mi and Mj) of the system and transition moments (μA and μB) of the individual chromophores: V = (Ei -E j){[(MiMj)(μA 2 -μB 2) -(μAμB)(M i 2 -Mj 2)]/[(Mi 2 -Mj 2)2 + 4(MiM j)2]}. These quantities are directly available from quantum mechanical calculations. As the estimated coupling accounts for both short-range and long-range interactions, this approach allows for the treatment of systems with short intermolecular distances, in particular, π-stacked chromophores. For a system of two identical chromophores, the coupling is given by V = (Ei -Ej)[(EiFj -E jFi)/(EiFj + EjF i)][1/(2 cos θ)] where Fi and Fj are the corresponding oscillator strengths and cos θ is determined by the relative position of the chromophores in the dimer. Thus, the coupling can be derived from purely experimental data. The developed approach is used to calculate the EET coupling and exciton delocalization in two π-stacks of pyrimidine nucleobases 5′-TT-3′ and 5′-CT-3′ showing quite different EET properties
dc.description.sponsorship
Financial support from MICINN (Ministry of Science and Innovation, Spain) was provided by grant CTQ 2011-26573
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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/jp410802d
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© Journal of Physical Chemistry C, 2014, vol. 118, p. 1478-1483
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Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.subject
dc.title
Estimation of electronic coupling for singlet excitation energy transfer
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.identifier.idgrec
024463
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1932-7455