Rotational energy transfer in HF(v = 2): Double resonance measurements and fitting law analysis

Journal Article · Sun May 01 04:00:00 EDT 1983 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.445481· OSTI ID:6050021

Copeland, R A; Crim, F F

Data from overtone vibration-laser double resonance experiments show extremely rapid rotational relaxation in HF (v = 2) for rotational states up to J = 6 and serve to test energy based fitting laws for rotational energy transfer rate constants. The observed rotational states equilibrate in less than a gas kinetic collision with some individual rates being more than twice the hard sphere collision rate. Energy based fitting laws reproduce the observed evolution of the state populations to within 30% but fail systematically for higher (J = 5 and 6) rotational levels. Fitting laws formulated for collisions between an atom and a molecule are virtually as successful as those for collisions between two molecules. The extracted rate constants show that multiple rotational quantum energy transfer is an important aspect of relaxation dynamics.

• Research Organization: Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706
• OSTI ID: 6050021
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 78:9; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
COLLISIONS
DOUBLE RESONANCE METHODS
ENERGY LEVELS
ENERGY TRANSFER
EXCITED STATES
HYDROFLUORIC ACID
HYDROGEN COMPOUNDS
INORGANIC ACIDS
MOLECULE COLLISIONS
MOLECULE-MOLECULE COLLISIONS
RELAXATION
ROTATIONAL STATES