US EPA

1297835 

Journal Article 

The effects of collision energy, vibrational mode, and vibrational angular momentum on energy transfer and dissociation in NO2+-rare gas collisions: an experimental and trajectory study 

Liu, J; Uselman, BW; Boyle, JM; Anderson, SL 

2006 

Yes 

Journal of Chemical Physics
ISSN: 0021-9606
EISSN: 1089-7690 

125 

13 

133115 

English 

17029441 

10.1063/1.2229207 

WOS:000241056600024 

A combined experimental and trajectory study of vibrationally state-selected NO2+ collisions with Ne, Ar, Kr, and Xe is presented. Ne, Ar, and Kr are similar in that only dissociation to the excited singlet oxygen channel is observed; however, the appearance energies vary by approximately 4 eV between the three rare gases, and the variation is nonmonotonic in rare gas mass. Xe behaves quite differently, allowing efficient access to the ground triplet state dissociation channel. For all four rare gases there are strong effects of NO2+ vibrational excitation that extend over the entire collision energy range, implying that vibration influences the efficiency of collision to internal energy conversion. Bending excitation is more efficient than stretching; however, bending angular momentum partially counters the enhancement. Direct dynamics trajectories for NO2+ + Kr reproduce both the collision energy and vibrational state effects observed experimentally and reveal that intracomplex charge transfer is critical for the efficient energy transfer needed to drive dissociation. The strong vibrational effects can be rationalized in terms of bending, and to a lesser extent, stretching distortion enhancing transition to the Kr+ -NO2 charge state.