Abstract
The quantitative application of source-irradiation ion cyclotron double resonance to the measurement of the relative rates of competing ion—molecule reactions is considered, with specific application illustrated for the kinetic scheme ▪ Theoretical and experimental grounds are presented for believing that the predominant origin of a normal double resonance effect is reactant ion ejection, and an expression is given for ion ejection as a function of irradiating field strength. A set of expressions is derived giving quantitative peak heights for the ionic species of Scheme I for both the single resonance and double resonance experiments. Experimental double resonance results at several irradiating field strengths are reported which support the theoretical model. Combining these results with a single resonance measurement of rate constant C 1, the rate constants determined are: C 1 = (7.5±1) × 10 −10 cm 3 molecule −1sec −1, C 2/ C 1 = 1.5 and C 3/ C 1 = 0.57.
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