On the performance of the Kohn-Sham orbital approach in the calculation of electron transfer parameters. the three state model
dc.contributor.author
dc.date.accessioned
2015-11-09T13:37:13Z
dc.date.available
2015-11-09T13:37:13Z
dc.date.issued
2014
dc.identifier.issn
1463-9076
dc.identifier.uri
dc.description.abstract
We have tested the performance of the Kohn-Sham orbital approach to obtain the electronic coupling and the energetics for hole transfer (HT) in the guanine-indole pair, using a three-state model. The parameters are derived from the simple DFT calculations with 10 different functionals, and compared with benchmark MS-CASPT2 calculations. The guanine-indole pair is a simple model for HT in DNA-protein complexes, which has been postulated as a protection mechanism for DNA against oxidative damage. In this pair, the first excited state of the indole radical cation has low energy (less than 0.3 eV relative to the ground state of the cation), which requires the application of very accurate quantum chemical methods and the invocation of a 3-state model. The Kohn-Sham orbital approach has been tested on six π stacked and three T-shaped conformers. It has been shown to provide quite accurate results for all ten tested functionals, compared to the reference MS-CASPT2 values. The best performance has been found for the long-range corrected CAM-B3LYP functional. Our results suggest that the Kohn-Sham orbital method can be used to estimate the excited state properties of radical cation systems studied using transient spectroscopy. Because of its accuracy and its low computational cost, the approach allows one to calculate relatively large models and to account for the effects of conformational dynamics on HT between DNA and a protein environment
dc.description.sponsorship
This work has been supported by grants CTQ2011-23441 and CTQ2011-26573 from the Spanish Ministerio de Economia y Competividad (MINECO), SGR0528 from the Catalan Agencia de Gestio d'Ajuts Universitaris i de Recerca (AGAUR), UNGI08-4E-003 and UNGI10-4E-801 from MINECO and the European Fund for Regional Development (FEDER), and the Xarxa de Referencia en Quimica Teorica i Computacional de Catalunya from AGAUR
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry (RSC)
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-23441/ES/NUEVOS ENFOQUES PARA EL ESTUDIO COMPUTACIONAL DE BIOMOLECULAS, INTERACCIONES DE ESPIN EN AGREGADOS METALICOS Y SISTEMAS MOLECULARES DE ALMACENAMIENTO DE HIDROGENO/
info:eu-repo/grantAgreement/MICINN//CTQ2011-26573/ES/MODELIZACION QUIMICO CUANTICA DE FOTOQUIMICA Y TRANSFERENCIA ELECTRONICA: SISTEMAS GRANDES, EFECTOS COLECTIVOS Y CONTROL OPTICO/
AGAUR/2009-2014/2009 SGR-528
info:eu-repo/grantAgreement/MEC//UNGI08-4E-003/ES/Clúster de PCs para cálculo intensivo en química cuántica/
info:eu-repo/grantAgreement/MICINN//UNGI10-4E-801/ES/Clúster de PCs para cálculo intensivo en química cuántica/
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c4cp02117g
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© Physical Chemistry Chemical Physics, 2014, vol. 16, núm. 32, p. 17154-17162
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Articles publicats (D-Q)
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Tots els drets reservats
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dc.title
On the performance of the Kohn-Sham orbital approach in the calculation of electron transfer parameters. the three state model
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
022122
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1463-9084