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

Literature Information

Publication Date 2015-10-08
DOI 10.1039/C5CP05400A
Impact Factor 3.676
Authors

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


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Abstract

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 τ = 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 (τ = 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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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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