To cite this version:C. Canuel, Mohamed Elhanine, M. Mons, F. Piuzzi, B. Tardivel, et al.. Time-resolved photoelectron and photoion fragmentation spectroscopy study of 9-methyladenine and its hydrates: a contribution to the understanding of the ultrafast radiationless decay of excited DNA bases.. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2006, 8, pp.3978-3987. <10.1039/b606437j>.
AbstractThe excited state dynamics of the purine base 9-methyladenine (9-MeAde) has been investigated by time-and energy-resolved photoelectron imaging spectroscopy and massselected ion spectroscopy both in vacuum and water-cluster environment. The specific probe processes used, namely a careful monitoring of time-resolved photoelectron energy distributions and of photoion fragmentation, together with the excellent temporal resolution achieved enable us to derive additional information on the nature of the excited (ππ*, nπ*, πσ*, triplet) states involved in the electronic relaxation of adenine. The two-step pathway we propose to account for the double exponential decay observed agrees well with the recent theoretical calculations. The near UV photophysics of 9MeAde is dominated by the direct excitation of the ππ* ( 1 L b ) state (lifetime of 100 fs), followed by internal conversion, proceeding to the nπ* state (lifetime in the ps range) via conical intersection. No evidence for the involvement of a πσ* or a triplet state was found. 9MeAde-water clusters have been studied, focussing onto the fragmentation of these species after the probe process. A careful analysis of the fragments allowed us to provide evidence for a double exponential decay profile for the hydrates. The very weak second component observed, however, leads to conclude to a very different photophysics as compared to the isolated base, assigned to a competition between i) a direct one-step decay of the initially excited state (ππ* L a and/or L b , stabilised by hydration) to the ground state and ii) a modified two-step decay scheme, qualitatively comparable to that occurring in the isolated molecule.