Energy randomisation. How much of rotational phase space is explored? How long does it take? Page: 1 of 30
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How much of Rotational Phase Space is explored?
How long does it take?
David S. Perry a
Department of Chemistry, University of Akron, Akron OH 44325-3601, USA
G. A. Bethardy, Michael J. Davis, and
Chemistry Division, Argonne National Laboratory, Argonne, IL 60439, USA.
Department of Chemistry, Sunchon National University, Sunchon,
Chunnam 540-742, South Korea.
a corresponding author
The assumption.that the internal energy of a molecule is randomised on a
time scale short compared to the reaction time is at the heart of modern theories of
unimolecular reaction. In applying such theories it is necessary to decide the
volume of phase space in which the energy is assumed to be randomised. The
question of whether the K rotational quantum number is conserved impacts on
that choice. The conceptual sequence from experimental spectra, through
analysis, and interpretation in terms of K relaxation is described below.
At low resolution, intramolecular vibrational energy randomisation results
in the broadening of the features of infrared absorption spectra. At high
resolution in bound systems, such broadened features are revealed to be clumps
of discrete lines, each of which is a transition to a molecular eigenstate. Since the
discrete lines can be assigned by spectroscopic means, the erroneous assignment
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Perry, D. S.; Bethardy, G. A.; Davis, M. J. & Go, J. Energy randomisation. How much of rotational phase space is explored? How long does it take?, article, December 1995; Illinois. (digital.library.unt.edu/ark:/67531/metadc668965/m1/1/: accessed January 21, 2019), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.