Improved relations for vibrational relaxation in gases

Explicit expressions are presented for calculating vibration-to-translation (VT) energy conversion probabilities, essential in molecular laser isotope separation. VT conversions in molecular collisions occur by two mechanisms: (1) high-energy impact transfers prevailing at higher temperatures, and (2) Van der Waals-bonding encounters followed by (pre-)dissociations at lower temperatures. While mechanism (1) has been studied for over fifty years culminating in the Schwartz Slawsky-Herzberg relation, a useful analytic expression for (2) has so far been lacking. An improved dimer formation theory developed by the author together with molecular pre-dissociation physics now provides a VT conversion relation for mechanism (2), which correctly predicts observations. (c) 2006 Elsevier B.V. All rights reserved.