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Single water solvation dynamics in the 4-aminobenzonitrile-water cluster cation revealed by picosecond time-resolved infrared spectroscopy

Miyazaki, Mitsuhiko; Nakamura, Takashi; Wohlgemuth, Matthias; Mitrić, Roland; Dopfer, Otto; Fujii, Masaaki

FG Lasermolekülspektroskopie und Umweltphysik

The dynamics of a solvent is important for many chemical and biological processes. Here, the migration dynamics of a single water molecule is triggered by the photoionization of the 4-aminobenzonitrile-water (4ABN-W) cluster and monitored in real time by picosecond time-resolved IR (ps TRIR) spectroscopy. In the neutral cluster, water is hydrogen-bonded to the CN group. When this CN-bound cluster is selectively ionized with an excess energy of 1238 cm(-1), water migrates with a lifetime of tau = 17 ps from the CN to the NH2 group, forming a more stable 4ABN(+)-W(NH) isomer with a yield of unity. By decreasing the ionization excess energy, the yield of the CN -> NH2 reaction is reduced. The relatively slow migration in comparison to the ionization-induced solvent dynamics in the related acetanilide-water cluster cation (tau = 5 ps) is discussed in terms of the internal excess energy after photoionization and the shape of the potential energy surface.
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