ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
A comprehensive study of the vibrational predissociation dynamics of the HCl dimer is reported. The predissociation lifetimes for three H–Cl stretch vibrationally excited states of (H35Cl)2 have been measured. Companion measurements for the H35Cl•H37Cl complex have also been made. These lifetimes range from 16(2) to 46(5) ns, lifetimes that are more than 106 times longer than the H–Cl stretch vibrational period. The correlated HCl(v′=0,j′)+HCl(v″=0,j″) fragment rotational state distributions have also been determined. These show a predominant dynamical bias that favors the production of j′,j″ pairs that maximize the rotational energy of the fragments and minimize their translational energy. The j′,j″ distribution is well described by a simple energy gap model of the dissociation. The results suggest a complex, for which there are substantial excursions from the equilibrium geometry, dissociation from a wide range of geometries, weak coupling of the H–Cl stretch vibrations to the dissociation coordinate, and a blurring of the distinction between hydrogen bonded and free HCl moieties. These results are consistent with theoretical studies of the HCl dimer potential energy surface. © 2000 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1286975
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