Overtone spectroscopy of H2O clusters in the vOH=2 manifold: Infrared-ultraviolet vibrationally mediated dissociation studies
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Spectroscopy and predissociation dynamics of (H2O)2 and Ar-H2O are investigated with vibrationally mediated dissociation (VMD) techniques, wherein vOH=2 overtones of the complexes are selectively prepared with direct infrared pumping, followed by 193 nm photolysis of the excited H2O molecules. As a function of relative laser timing, the photolysis breaks H2O into OH and H fragments either (i) directly inside the complex or (ii) after the complex undergoes vibrational predissociation, with the nascent quantum state distribution of the OH photofragment probed via laser-induced fluorescence. This capability provides the first rotationally resolved spectroscopic analysis of (H2O)2 in the first overtone region and vibrational predissociation dynamics of water dimer and Ar-water clusters. The sensitivity of the VMD approach permits several vOH=2 overtone bands to be observed, the spectroscopic assignment of which is discussed in the context of recent anharmonic theoretical calculations. 鲰05 American Institute of Physics
Journal of Chemical Physics
Copyright 2005 American Institute of Physics: Reproduced in accordance with the copyright policy of the publisher: This journal is available online - use hypertext links.