Počet záznamů: 1
The Charge-Transfer States in a Stacked Nucleobase Dimer Complex: A Benchmark study
0364672 - UOCHB-X 2012 RIV US eng J - Článek v odborném periodiku
Aquino, A. J. A. - Nachtigallová, Dana - Hobza, Pavel - Truhlar, D. G. - Hättig, Ch. - Lischka, Hans
The Charge-Transfer States in a Stacked Nucleobase Dimer Complex: A Benchmark study.
Journal of Computational Chemistry. Roč. 32, č. 7 (2011), s. 1217-1227 ISSN 0192-8651
Grant CEP: GA MŠk LC512
Grant ostatní: NSF(US) CHE09-56776
Výzkumný záměr: CEZ:AV0Z40550506
Klíčová slova: charge transfer * excited states * coupled cluster * DFT * stacked nucleobases
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 4.583, rok: 2011
Electronic singlet excitations of stacked adenine–thymine (AT) and guanine–cytosine (GC) complexes have been investigated with respect to local excitation and charge-transfer (CT) characters. Potential energy curves for rigid displacement of the nucleobases have been computed to establish the distance dependence of the CT states. ADC(2) method served as reference approach for comparison to a selected set of density functionals used within the TD-DFT. Particular attention was dedicated to the performance of the recently developed family of M06 functionals. The calculations for the stacked complexes show that at the ADC(2) level, the lowest CT state is S6 for the AT and as S4 for the GC pair. At the reference geometry, the actual charge transferred is found to be 0.73 e for AT. In case of GC, this amount is much smaller (0.17 e). With increasing separation of the two nucleobases, the CT state is strongly destabilized. The M06-2X version provides a relatively good reproduction of the ADC(2) results. It avoids the serious overstabilization and overcrowding of the spectrum found with the B3LYP functional. On the other hand, M06-HF destabilizes the CT state too strongly.
Trvalý link: http://hdl.handle.net/11104/0200095