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Journal of Physical Chemistry, Vol.99, No.37, 13748-13754, 1995
Mode-Selective and Bond-Selective Reactions of Chlorine Atoms with Highly Vibrationally Excited H2O and Hod
The measured OH product state distribution from the Cl + H2O (04](-)) --> HCl + OH reaction reveals an energy disposal pattern that is similar to that in the analogous H + H2O (04](-)) --> H-2 + OH reaction. Of the 9700 cm(-1) available energy, approximately 6% appears in internal OH excitation, approximately 21% in product translation, and the remainder (about 73%) appears as internal HCl excitation. The result that most of the available energy appears as internal energy of the newly formed diatomic molecule supports a spectator picture in which the old bond does not participate in the reaction. We measure the bond-selective branching ratio for the Cl + HOD (4 upsilon(OH)) reaction and fmd that initial excitation of the O-H bond favors the HCl + OD product channel by at least a factor of 40. Measurements of the relative reactivity of water molecules prepared in the 04](-), 04](+) and 03](-)2] local mode vibrational states suggest that all three vibrational modes enhance the reactivity by approximately the same factor.
Keywords:CONTROLLING BIMOLECULAR REACTIONS;A-X SYSTEM;HYDROGEN-ATOMS;ENERGY DISPOSAL;CHEMISTRY;WATER;OH;STATE;DISTRIBUTIONS;EXAMPLE