Rose, Todd S. and Rosker, Mark J. and Zewail, Ahmed H. (1989) Femtosecond real-time probing of reactions. IV. The reactions of alkali halides. Journal of Chemical Physics, 91 (12). pp. 7415-7436. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:ROSjcp89
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The photodissociation dynamics of some alkali halides are explored via the method of femtosecond transition-state spectroscopy (FTS). The alkali halide dissociation reaction is influenced by the interaction between the covalent and the ground state ionic potential energy surfaces (PES), which cross at a certain internuclear separation. Depending upon the adiabaticity of the PES, the dissociating fragments may be trapped in a well formed by the avoided crossing of these surfaces. Here, we detail the FTS results of this class of reactions, with particular focus on the reaction of sodium iodide: NaI*-->[Na---I]°* -->Na+I. As in our first report [T. S. Rose, M. J. Rosker, and A. H. Zewail, J. Chem. Phys. 88, 6672 (1988)], we observe the dynamical motion of the wave packet along the reaction coordinate and the crossing between the covalent and ionic surfaces. The studies presented here characterize the effects of various experimental parameters, including pump and probe wavelengths, on the dynamics of the dissociation and its detection. Comparisons of the results with classical and quantum mechanical calculations are also presented.
|Additional Information:||Copyright © 1989 American Institute of Physics. Received 30 June 1989; accepted 15 August 1989. This work was supported by Air Force Office of Scientific Research. Contribution No. 7966. We wish to thank Martin Gruebele for his helpful comments on the manuscript.|
|Subject Keywords:||PHOTODISSOCIATION, FS RANGE, DYNAMICS, ALKALI HALIDES, POTENTIAL ENERGY SURFACES, CHEMICAL BONDS, REACTION INTERMEDIATES, SPECTROSCOPY|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Archive Administrator|
|Deposited On:||03 Jun 2008|
|Last Modified:||26 Dec 2012 10:03|
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