DNA bases; ionization energies; ab initio calculations
Abstract :
[en] The ionization of the four DNA bases is investigated by means of ab initio calculations. Accurate values of the gas-phase vertical and adiabatic ionization potentials (IP) are obtained at the MP2/6-31G(2d(0.8, alpha(d)), p) level of theory. The need of introducing extra polarization to the standard 6-31G(d, p) basis set is demonstrated by test calculations and an optimal value of alpha(d) = 0.1 is obtained. Ionization to electronically excited radical cations is also considered. The low-lying excited states of the cations are characterized for the first time. The topology of the corresponding potential energy surfaces is qualitatively described in terms of the stationary points ( minima and saddle points) located on these surfaces. A conical intersection is characterized for the first time on the ground-state potential energy surface of all cations. It arises from the crossing of the adiabatic surfaces of the ground and first excited state at planar geometries. A nonplanar minimum is observed for the cytosine cation only. The geometry and electronic changes occurring along these surfaces are analyzed, leading to a comparison between the different nucleobase cations. The study of larger ionized systems related to DNA is rendered possible thanks to the optimized medium size basis set proposed in this work, as exemplified by the calculation of the IP of a stacked dimer of guanines.
Disciplines :
Chemistry Physics
Author, co-author :
Cauët, Emilie
Dehareng, Dominique ; Université de Liège - ULiège > Centre d'ingénierie des protéines
Lievin, Jacques
Language :
English
Title :
Ab initio study of the ionization of the DNA bases: Ionization potentials and excited states of the cations
Publication date :
27 July 2006
Journal title :
Journal of Physical Chemistry. A
ISSN :
1089-5639
eISSN :
1520-5215
Publisher :
Amer Chemical Soc, Washington, United States - Washington
Volume :
110
Issue :
29
Pages :
9200-9211
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
BELSPO - Service Public Fédéral de Programmation Politique scientifique [BE] DGENORS - Communauté française de Belgique. Direction générale de l’Enseignement non obligatoire et de la Recherche scientifique [BE] FRFC - Fonds de la Recherche Fondamentale Collective [BE] COST - European Cooperation in Science and Technology [BE]
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