Dependence of the four-atom reaction HBr + OH → Br + H2O on temperatures between 20 and 2000 K.
A quasiclassical trajectory method is used to study the temperature dependence of HBr + OH → Br + H2O using analytic forms of two-, three-, and four-body and long-range interaction potentials. Below 300 K, the reaction is attraction-driven and occurs through formation of a collision complex BrH···OH, which is sufficiently long-lived to enhance H atom tunneling. Strong negative temperature dependence of the complex-mode rate is found between 20 and 300 K, consistent with experimental data reported by various authors. Above 300 K, the reaction occurs primarily through a direct-reaction mechanism. The sum of the complex- and direct-mode rates is shown to describe the reaction over the wide range 20-2000 K. The primary kinetic isotope effect is nearly constant with the normal H reaction faster by a factor of ∼1.7 over the entire temperature range. The product energy distribution in vibration, rotation, and translation at 300 K is found to be 48, 8, and 44%, respectively. The 1:1 resonance leads to efficient flow of energy between the stretching modes. Less than a quarter of the H2O vibrational energy deposits in the bending mode through intramolecular flow from the two stretching modes.
†Department of Chemistry Education, Chonnam National University, Gwangju 500-757, Korea.
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Ree
‡Department of Chemistry, Inha University, Incheon 402-751, Korea.
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Kim
§Department of Chemistry, University of Nevada, Reno, Nevada 89557 United States.
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Shin