The decay mechanism of photoexcited guanine - A nonadiabatic dynamics study

Mario Barbatti (1) , Jaroslaw J. Szymczak (2) , Adelia J. A. Aquino (3) , Dana Nachtigallova (4) , Hans Lischka (5)

1 Max-Planck-Institut für Kohlenforschung (Coal Research)
2 Universität Wien
3 Institute for Theoretical Chemistry
4 CAS - Czech Academy of Sciences [Prague]
5 Institute for theoretical Chemistry

Ab initio surface hopping dynamics calculations were performed for the biologically relevant tautomer of guanine in gas phase excited into the first pi pi* state. The results show that the complete population of UV-excited molecules returns to the ground state following an exponential decay within similar to 220 fs. This value is in good agreement with the experimentally obtained decay times of 148 and 360 fs. No fraction of the population remains trapped in the excited states. The internal conversion occurs in the pi pi* state at two related types of conical intersections strongly puckered at the C2 atom. Only a small population of about 5% following an alternative pathway via a n pi* state was found in the dynamics. (c) 2011 American Institute of Physics. [doi:10.1063/1.3521498]

Domains: Chemical Sciences; Theoretical and/or physical chemistry

Mario Barbatti, Jaroslaw J. Szymczak, Adelia J. A. Aquino, Dana Nachtigallova, Hans Lischka. The decay mechanism of photoexcited guanine - A nonadiabatic dynamics study. Journal of Chemical Physics, 2011, 134 (1), pp.014304. ⟨10.1063/1.3521498⟩. ⟨hal-01415206⟩