Energy partitioning in two kinds of NO molecules generated from the reaction of O(D-1) with N2O: Vibrational state distributions of "new" and "old" NO's
H. Akagi et al., Energy partitioning in two kinds of NO molecules generated from the reaction of O(D-1) with N2O: Vibrational state distributions of "new" and "old" NO's, J CHEM PHYS, 111(1), 1999, pp. 115-122
The reaction of O(D-1) with N2O produces two kinds of NO molecules, the "ol
d" one which originally exists in N2O and the "new" one which includes the
attacking O atom. Using the isotopically labeled reagent, we determined the
vibrational state distributions of these NO's (X (2)Pi; v=0-17) separately
. To obtain the distributions, two types of experiments were performed with
the laser-induced fluorescence (LIF) technique via the NO A<--X and B<--X
transitions. First, the relative populations of NO molecules (the sum of th
e two kinds of NO's) in v=0-11 levels were measured with unlabeled reagents
. Then, isotopically labeled reaction, O-18(D-1)+(N2O)-O-16-->(NO)-O-18+(NO
)-O-16, was utilized to determine the relative ratio between the two kinds
of NO's in the vibrational levels of v=0-5 and 12-15. Combining the above r
esults with previously determined vibrational state distribution of NO in h
igh vibrational levels (v=11-17) [J. Chem. Soc., Faraday Trans. 94, 1575 (1
998)], we were able to obtain a complete set of vibrational state distribut
ions. It was found that the old NO dominantly populated in v=0 and 1 wherea
s the new NO extended its population toward higher vibrational levels (v=4-
15). However, in high vibrational levels, the old NO still have a considera
ble population due to the rapid energy transfer to the old NO. The observed
efficient energy transfer to the old NO is attributed to the absence of li
ght atoms in the present reacting system. Compared with the system includin
g hydrogen atoms, the state density and the momentum coupling among the vib
rational modes are much larger and accelerate the energy redistribution in
spite of the short lifetime. (C) 1999 American Institute of Physics. [S0021
-9606(99)02225-4].