Near-resonant rotation-vibration energy transfer in atom-diatom collisions
In this dissertation, a theory of vibration-rotation (V-R) energy transfer in atom-vibrating-rotor collisions is formulated by a simple extension of the Arthurs and Dalgarno atom-rigid-rotor theory, and V-R transition probabilities, cross sections and rate constants are found from solutions to a set of coupled differential equations. The theory is tested on two near-resonant V-R energy transfer processes. First, the rate constant for the (υ=0, j=20 <– υ=1, j=15) transition in Ar-OH(A^2 Σ^+) is calculated in the infinite-order sudden approximation and in the distorted-wave approximation at 360°K. The results agree with experiment and indicate that the transition is direct and first-order. Second, cross sections for the (υ=1, j=7 <– υ=0, j=11) excitation in Li^+ -H_2(X^1 Σ_g^+) are obtained in the exponential distorted-wave approximation at 14,000°K. The calculated cross sections are larger than those of neighboring off-resonant V-R and non-V-R transitions. It is concluded that near-resonant V-R energy transfer is an important process in atom-diatom collisions.
College and Department
Chemistry and Biochemistry
BYU ScholarsArchive Citation
Smith, Wesley Dexter, "Near-resonant rotation-vibration energy transfer in atom-diatom collisions" (1973). Theses and Dissertations. 8357.
Collisions (Nuclear physics), Particles (Nuclear physics)