Single collision gas-surface vibrational energy transfer in reactive systems. Variation of initial energy distribution

Article abstract of DOI:10.1063/1.443266

The initial vibrational energy distribution of molecules that collide with a hot surface has been varied.The effect of the variation on the collisional reaction probability (P_c) has been studied under single collision conditions.These experiments provide a more sensitive test of the relative suitability of various analytical forms for the collisional transition probability matrix P than has been achieved previously in earlier VEM experiments.The reaction system is the isomerization of cyclobutene to 1,3-butadiene.A seasoned fused quartz surface was used over the temperature range T_r = 600-900 K.Variation of the initial vibrational energy population vector of cyclobutene molecules was made by change of their initial temperature T_c in the range 273-620 K.The experimental collisional efficiency β₁ declined from 0.31 to 0.013 over the combination temperature ranges T_r, T_c = 600, 500 to 900, 273. Stochastic models of the vibrational transition probabilitywere fitted to the data and provided values for the average amount of energy (<ΔE'>E₀) transferred from the hot molecules in a down transition from the threshold energy level E₀; Gaussian or Boltzmann exponential forms of P prove to be the most suitable to fit the data.Calculated values, <ΔE'>E₀ on the basis of a Gaussian function model for P declined from 5600 to 3700 cm^-1 with increase in the surface temperature from 600 to 900 K.

Full text of DOI:10.1063/1.443266

Single collision gassurface vibrational energy transfer in reactive systems. Variation of
initial energy distribution
R. Arakawa, D. F. Kelley, and B. S. Rabinovitch
Citation: The Journal of Chemical Physics 76, 2384 (1982); doi: 10.1063/1.443266
View online: http://dx.doi.org/10.1063/1.443266
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/76/5?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
155.33.148.196 On: Wed, 03 Dec 2014 22:36:15

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
155.33.148.196 On: Wed, 03 Dec 2014 22:36:15

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
155.33.148.196 On: Wed, 03 Dec 2014 22:36:15

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
155.33.148.196 On: Wed, 03 Dec 2014 22:36:15

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
155.33.148.196 On: Wed, 03 Dec 2014 22:36:15

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
155.33.148.196 On: Wed, 03 Dec 2014 22:36:15