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Further insight into the tunneling contribution to the vibrational relaxation of NO in Ar.

MPS-Authors
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Dashevskaya,  E.I.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

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Litvin,  I.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

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Nikitin,  E. E.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

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Troe,  J.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

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Citation

Dashevskaya, E., Litvin, I., Nikitin, E. E., & Troe, J. (2015). Further insight into the tunneling contribution to the vibrational relaxation of NO in Ar. Journal of Chemical Physics, 142(16): 164310. doi:10.1063/1.4919126.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0027-8317-6
Abstract
Tunneling corrections to Landau-Zener rate coefficients for the vibrational relaxation NO(X 2Π, v = 1) + Ar → NO(X 2Π, v = 0) + Ar between 300 and 2000 K are determined employing ab initio potential energy surfaces calculated by the code provided by Alexander [J. Chem. Phys. 111, 7426 (1999)]. The calculations use a reaction coordinate approach and lead to vibronically nonadiabatic transition probabilities within the generalized Airy approximation as extended to the WKB underbarrier Landau-Lifshitz limit. The calculations confirm experimental evidence for an onset of major tunneling contributions to the relaxation rate at temperatures below about 900 K and rationalize large tunneling contributions at 300 K. These effects increase the rate coefficients by several orders of magnitude over the uncorrected Landau-Zener values and remove the large gap between the latter and experimental results.