Abstract
The reaction of neopentyl radicals with molecular oxygen (O/sub 2/) in the gas phase has been studied between 266 and 374 K by following the pseudo-first-order decay of the radicals with a photoionization mass spectrometer. The rate constants exhibit a negative temperature dependence; k/sub 1/ = /2.1 x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1//(T/300 K)/sup -(2.1 +/- 0.4)/. The rate constant measured at room temperature is larger than the vale reported previously by about one-third. Conventional transition-state theory is not able to rationalize both the negative temperature dependence and the absolute magnitude of the rate constant. An adiabatic channel model calculation can be made to give good agreement with the experimental rate constant at different temperatures.
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