Ultralow temperature kinetics of neutral-neutral reactions. The technique and results for the reactions CN+O2 down to 13 K and CN+NH3 down to 25 K

Article abstract of DOI:10.1063/1.467227

An entirely new experimental method is described which enables the rate constants of neutral-neutral gas-phase reactions to be measured at ultralow temperatures.The measurements are made by applying the pulsed laser photolysis (PLP), laser-induced fluorescence (LIF) technique of studying the kinetics of free radical reactions in the ultracold environment provided by the gas flow in a Cinetique de Reaction en Ecoulement Supersonique Uniforme (CRESU) apparatus.The experimental method is described in some detail and its application and limitations are discussed.Results are reported for the reactions of CN radicals with O2 and NH3.For reaction (1) between CN and O2 data are reported for the temperature range T=13-295 K and the rate constants are well-matched by the expression k₁(T)=(2.49+/-0.17)*10^-11 (T/298)^{(-0.63+/-0.04)} cm³ molecule^-1 s^-1.For reaction (2) between CN and NH3, rate constants in the temperature range T=25-295 K fit the expression k₂(T)=(2.77+/-0.67)*10^-11 (T/298)^{(-1.14+/-0.15)} cm³ molecule^-1 s^-1.The kinetic data are discussed in terms of the latest quantum chemical and reaction rate theories for these systems.

Full text of DOI:10.1063/1.467227

Ultralow temperature kinetics of neutral–neutral reactions. The technique and
results for the reactions CN+O2 down to 13 K and CN+NH3 down to 25 K
I. R. Sims, J.L. Queffelec, A. Defrance, C. RebrionRowe, D. Travers, P. Bocherel, B. R. Rowe, and I. W. M.
Smith
Citation: The Journal of Chemical Physics 100, 4229 (1994); doi: 10.1063/1.467227
View online: http://dx.doi.org/10.1063/1.467227
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/100/6?ver=pdfcov
Published by the AIP Publishing
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194.47.65.106 On: Wed, 15 Oct 2014 17:50:23

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194.47.65.106 On: Wed, 15 Oct 2014 17:50:23

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