Rotational energy transfer in HF(v=2): Energy corrected sudden approximation scaling relations applied to double resonance measurements

Abstract

Applying scaling relations based on the energy corrected sudden (ECS) approximation to a large set of laser double resonance measurements of HF self-relaxation allows the time evolution of individual rotational states from J′=2 to 6 to be described by only a few fitting parameters and permits extraction of state-to-state energy transfer rate constants. Obtaining a qualitatively correct description of the data requires inclusion of a significant (∼25%) multiple rotational quantum pathway (‖ΔJ‖≥2). The ECS approximation based scaling relation seems to provide a better description of the rotational energy transfer for high rotational levels (J′=5 and 6) than do relations based solely on energy defect. Comparing the double resonance results to those of linewidth analysis shows differences that may arise from the sensitivity of the measurements to different aspects of the energy transfer dynamics. Extrapolating the rate constants obtained by fitting the double resonance data on low rotational levels (J′≤6) yields good agreement with recent independent measurements on J′=11 to 14 in HF(v=0).