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On the performance of the Kohn-Sham orbital approach in the calculation of electron transfer parameters. the three state model

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

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

© Physical Chemistry Chemical Physics, 2014, vol. 16, núm. 32, p. 17154-17162

Royal Society of Chemistry (RSC)

Author: Butchosa Robles, Cristina
Simon i Rabasseda, Sílvia
Blancafort San José, Lluís
Voityuk, Alexander A.
Date: 2014
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
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
Format: application/pdf
ISSN: 1463-9076 (versió paper)
1463-9084 (versió electrònica)
Document access: http://hdl.handle.net/10256/11469
Language: eng
Publisher: Royal Society of Chemistry (RSC)
Collection: MICINN/PN 2012-2014/CTQ2011-23441
MICINN/PN 2012-2014/CTQ2011-26573
AGAUR/2009-2014/2009 SGR-528
MEC/2008/UNGI08-4E-003
MICINN/2010/UNGI10-4E-801
Reproducció digital del document publicat a: http://dx.doi.org/10.1039/c4cp02117g
Articles publicats (D-Q)
Is part of: © Physical Chemistry Chemical Physics, 2014, vol. 16, núm. 32, p. 17154-17162
Rights: Tots els drets reservats
Subject: Química de l’estat excitat
Excited state chemistry
Química quàntica
Quantum chemistry
Orbitals moleculars
Molecular orbitals
Title: On the performance of the Kohn-Sham orbital approach in the calculation of electron transfer parameters. the three state model
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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