An evaluation of the role of internal energy and translational energy in the endothermic proton transfer reaction of N2H+ with Kr

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Abstract
The Innsbruck SIDT (selected ion drift tube), now modified to include an octupole guided beam region, has been utilized to investigate the title reaction using both virbationally excited and ground state N2H+. Rate constants measured for three distinguishable proton transfers at a field strength of 40 Td are 1.1×10−9, 2.7×10−10, and 1.3×10−11 cm3 s−1. These are assigned to the exothermic proton transfer reaction N2H+ (X,v=2)+Kr→KrH++N2 and the endothermic reactions of N2H+ (X,v=1) and N2H+ (X,v=0), respectively. This assignment is supported by studies of the kinetic energy dependence of the rate coefficients and the collisonal relaxation of excited N2H+ ions with N2. The latter process is characterized by a large rate coefficient kr=3×10−10 cm3 s−1 approximately one‐third the collision rate coefficient.