Minimum Energy Structures of Br2-ArN Clusters: Implications for Dynamics
The dynamics of photexcited dihalide species such as I2 has been extensively studied (1) in small van der Waals molecules with emphasis placed on the role of intramolecular energy transfer (2). In fluids, the geminate recombination dynamics of I2 excited to several electronic states has been studied both experimentally by picosecond spectroscopy and theoretically by molecular dynamics (MD) and other techniques (3), In order to bridge the gap between van der Waals molecules and condensed phases it is necessary to study small clusters of between 5 and 100 molecules in molecular beams. Our previous MD simulation study of photoexcitation dynamics of Br2ArN neutrals under beam condition demonstrated a gradual transition between the small molecule limit and the condensed phase limit as the numberof argon atoms was increased from 6 to 70 (4). For clusters of less than about 20 atoms, the Br2 caging dynamics is extremely sensitive to cluster geometry and loss of argon atoms occurs by impulsive energy transfer from Br2. For two shell cluster (70 atoms), loss of argon occurs by evaporation after the whole cluster is heated.
KeywordsMonte Carlo Argon Atom Minimum Energy Structure Intramolecular Energy Transfer Pentagonal Ring
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