title: Role of electron-driven proton-transfer processes in the excited-state deactivation of the adenine-thymine base pair.
abstract: Exploratory electronic structure calculations have been performed with the CC2 (simplified singles and doubles coupled-cluster) method for two conformers of the adenine (A)-thymine (T) base pair, with emphasis on excited-state proton-transfer reactions. The Watson-Crick conformer and the most stable (in the gas-phase) conformer of the A-T base pair have been considered. The equilibrium geometries of the ground state and of the lowest excited electronic states have been determined with the MP2 (second-order Møller-Plesset) and CC2 methods, respectively. Vertical and adiabatic excitation energies, oscillator strengths, and dipole moments of the excited states are reported. Of particular relevance for the photochemistry of the A-T base pair are optically dark (1)pipi* states of charge-transfer character. Although rather high in energy at the ground-state equilibrium geometry, these states are substantially lowered in energy by the transfer of a proton, which thus neutralizes the charge separation. A remarkable difference of the energetics of the proton-transfer reaction is predicted for the two tautomers of A-T: in the Watson-Crick conformer, but not in the most stable conformer, a sequence of conical intersections connects the UV-absorbing (1)pipi* state in a barrierless manner with the electronic ground state. These conical intersections allow a very fast deactivation of the potentially reactive excited states in the Watson-Crick conformer. The results provide evidence that the specific hydrogen-bonding pattern of the Watson-Crick conformer endows this structure with a greatly enhanced photostability. This property of the Watson-Crick conformer of A-T may have been essential for the selection of this species as carrier of genetic information in early stages of the biological evolution.
authors.affiliation: Institute of Physics, Polish Academy of Sciences, PL-02668 Warsaw, Poland.
authors.forename: Serhiy
authors.initials: S
authors.lastname: Perun
authors.forename: Andrzej L
authors.initials: AL
authors.lastname: Sobolewski
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Domcke
mesh_terms: D000225:Adenine / Q000737:chemistry*; D020029:Base Pairing; D004583:Electrons; D008958:Models, Molecular; D010777:Photochemistry; D011522:Protons; D013941:Thymine / Q000737:chemistry*
chemical_list: D011522:Protons; D000225:Adenine; D013941:Thymine