Skip to main content
U.S. flag

An official website of the United States government

Official websites use .gov
A .gov website belongs to an official government organization in the United States.

Secure .gov websites use HTTPS
A lock ( ) or https:// means you’ve safely connected to the .gov website. Share sensitive information only on official, secure websites.

Vibrational Enhancement of the Charge Transfer Reaction Rate of N2+(v=0-4) with Kr at Thermal Energies



S Kato, J A. de Gouw, C D. Lin, V M. Bierbaum, S R. Leone


The charge transfer reaction of N2+(v=0-4) + KR->N2 + Kr+ is studied at thermal energy as a function of vibrational excitation in the reactant ion. A selected-ion flow tube technique coupled with laser-induced fluorescence detection is used to measure the vibrationally specific rate constants. A dramatic vibrational enhancement is observed; measured rate constants are 1.0 ( O.6) x 10-12, 2.8 ( O.3) x 10-12, 2.1 ( O.2) x 10-11, 5.1 ( O.2) x 10-11 and 8.3 ( O.4) x 10-11 cm3 molecule-1 s-1 for v=0,1,2,3 and 4 respectively. Mass spectrometric kinetics experiments are also performed to confirm that vibrational relaxation, N2+(v) + Kr->N2+(v'2(v'=O) + Kr+(2P1) states), yet the reaction is enhanced when the apparent energy mismatch is greater for the vibrationally excited reactant. A simple model is proposed to explain the experimental results at thermal energies (< <1 eV). The model assumes that only the most enerL7v-resonant exothermic transitions, N2+(v) + Kr->N2(v+3) + Kr+ (-P1), occur within the duration of the ion-molecule collision complex and that the charge transfer takes place at probabilities governed by the corresponding Franck-Condon factors. However, the Franck-Condon factors are modified by a trial displacement of 0.02 A to accountfor the changes in vibrational wave functions of N2+ and N2 during a close approach of the (N2-Kr)+ pair; this method gives an excellent description of the experimental results.
Journal of Chemical Physics


charge transfer, ion-molecule reaction, krpton, laser fluorescence, nitrogen


Kato, S. , de Gouw, J. , Lin, C. , Bierbaum, V. and Leone, S. (2021), Vibrational Enhancement of the Charge Transfer Reaction Rate of N<sub>2</sub><sup>+</sup>(v=0-4) with Kr at Thermal Energies, Journal of Chemical Physics (Accessed June 19, 2024)


If you have any questions about this publication or are having problems accessing it, please contact

Created October 12, 2021