Measurement of the V-T energy transfer rates of highly excited 2A1 NO2

Article abstract of DOI:10.1063/1.466797

Production of electronic ground state NO2 (²A₁) from 248 nm photolysis of HNO3 was detected by laser induced fluorescence (LIF).A growth in the LIF signal was observed following the photolysis and has been interpreted as the relaxation of NO2 through the higher vibrational levels of the X(²A₁) state; an energy region where the probe laser photodissociates the NO2 instead of inducing fluorescence.The rate coefficients for NO2 relaxation through these high vibrational levels were determined by fits of time resolved LIF signal to a stepladder kinetic model.The results of the kinetic analysis suggest that the observed relaxation begins at the ²B₂ threshold near 9500 cm^-1 and extends downward through approximately 5 vibrational levels of the ground electronic surface.The derived quenching rate coefficients (in units of 10^-12 cm³ molecule^-1 s^-1) are 0.51+/-0.05, 1.0+/-0.1, 1.4+/-0.2, 2.6+/-0.6, and 8.7+/-1.1 for Ar, He, N2, O2, and CO2 collision partners, respectively.The discrepancies between these coefficients and previous literature values are rationalized in terms of a dependence of the vibrational relaxation rate on total internal energy.

Full text of DOI:10.1063/1.466797

Measurement of the V–T energy transfer rates of highly excited 2 A 1 NO2
Troy L. Mazely, Randall R. Friedl, and Stanley P. Sander
Citation: The Journal of Chemical Physics 100, 8040 (1994); doi: 10.1063/1.466797
View online: http://dx.doi.org/10.1063/1.466797
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/100/11?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:
147.143.2.5 On: Sat, 20 Dec 2014 12:38:42

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:
147.143.2.5 On: Sat, 20 Dec 2014 12:38:42

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:
147.143.2.5 On: Sat, 20 Dec 2014 12:38:42

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:
147.143.2.5 On: Sat, 20 Dec 2014 12:38:42

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:
147.143.2.5 On: Sat, 20 Dec 2014 12:38:42

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:
147.143.2.5 On: Sat, 20 Dec 2014 12:38:42