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Title: Wave packet dynamics of the N({sup 4}S){plus}O{sub 2}(X{sup 3}{summation}{over g}){r_arrow}NO(X{sup 2}{Pi}){plus}O({sup 3}P) reaction on the X{sup 2}A' potential energy surface.

We report three-dimensional quantum calculations of total angular momentum J = 0 reaction probabilities, J-shifting cross sections, and rate constants of the title reaction. Employing the real wave packet approach, we propagate wave packets corresponding to several O{sub 2}(v,j) initial levels on the X{sup 2}A' potential surface of Sayos et al. As collision energy increases, the average probabilities first increase monotonically and then become nearly constant, while the cross sections rise in the overall energy range. Numerous probability resonances point out the formation of NOO collision complexes and NO final states. Rotational excitation in O{sub 2} decreases the collisional energy thresholds and enhances the state-resolved rate constants, mainly at low temperature. O{sub 2} vibrational excitation inhibits the reactivity, although the energy thresholds are still reduced. With respect to previous quasiclassical and mixed quantum-classical studies, we obtain lower thresholds and cross sections but similar rate constants, which are however lower than experimental rates. By inspection of the average properties of the wave packets, we suggest a qualitative reaction mechanism, we propose a modified J-shifting approximation, and we find a possible explanation of the low quantum reactivity on the present potential.
Authors:
; ; ; ; ; ;
Publication Date:
OSTI Identifier:
949237
Report Number(s):
ANL/CHM/JA-38963
Journal ID: ISSN 0021-9606; JCPSA6; TRN: US201012%%38
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Chem. Phys.; Journal Volume: 115; Journal Issue: 7 ; Aug. 15, 2001
Research Org:
Argonne National Laboratory (ANL)
Sponsoring Org:
SC; FOR
Country of Publication:
United States
Language:
ENGLISH
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ANGULAR MOMENTUM; CROSS SECTIONS; ENERGY RANGE; EXCITATION; POTENTIAL ENERGY; PROBABILITY; REACTION KINETICS; WAVE PACKETS