Rotational excitation of symmetric top molecules by collisions with atoms. II. Infinite order sudden approximation

Journal Article · Mon Jan 15 04:00:00 EST 1979 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.437515· OSTI ID:6363627

Green, S

The infinite order sudden approximation is extended to rotational excitation of symmetric tops by collisions with atoms. The formalism is developed first for ''primitive'' or ''one-ended'' tops. The proper parity adapted linear combinations which describe real rotors are then considered. Modifications needed for asymmetric rigid rotors are noted briefly. For all of these cases generalized spectroscopic relaxation cross sections are discussed; these include degeneracy averaged state-to-state integral cross sections and pressure broadening cross sections as special cases. In the IOS formalism these cross sections factor into dynamical terms which contain all the system dependent collision information and spectroscopic coefficients which contain the dependence on rotational levels and angular momentum coupling. This factorization is similar to that obtained for linear rotors, but differs insofar as the dynamical factors cannot all be expressed in terms of single state-to-state cross sections and insofar as the generalized cross sections are no longer necessarily real quantities. IOS calculations for NH/sub 3/--He and H/sub 2/CO--He have been performed to compare with earlier, more accurate calculations. Both of these systems provide fairly severe tests since they have rather widely spaced energy levels with only a few levels accessible at thermal energies whereas the IOS approximation should be best for the opposite case of many closely spaced levels. Nevertheless, the IOS approximation is found to provide a reasonably accurate description for these systems. Finally, implications of the IOS factorization for the interpretation of microwave double resonance experiments for these systems is considered.

• Research Organization: NASA Goddard Institute for Space Studies, New York, New York 10025
• OSTI ID: 6363627
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 70:2; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
ALDEHYDES
AMMONIA
ATOM COLLISIONS
ATOM-MOLECULE COLLISIONS
COLLISIONS
CROSS SECTIONS
CRYOGENIC FLUIDS
ELEMENTS
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
FLUIDS
FORMALDEHYDE
HELIUM
HYDRIDES
HYDROGEN COMPOUNDS
MOLECULE COLLISIONS
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NONMETALS
ORGANIC COMPOUNDS
RARE GASES
ROTATIONAL STATES
SUDDEN APPROXIMATION