Kinetics of the vibrational relaxation of the HF–N2 system

Abstract

Based on the suggestion that $\mathrm{V‐V}$ transfers may be important in the vibrational relaxation of the ${\mathrm{HF–N}}_2$ system (Ref. 3), the experimental data for this system (Ref. 1) have been re‐examined using the STK (Ref. 4) equations. A nonlinear regression analysis has resulted in the determination of ${\tau }_{{\mathrm{N}}_2\mathrm{–HF}}^{\nu }$ and ${\tau }_{{\mathrm{N}}_2\mathrm{–HF}}$ . Sentman's theory agrees very well with the $\mathrm{V‐V}$ relaxation time, but the $V\mathrm{–R–T}$ rate is an order of magnitude faster than the theoretical prediction. These results suggest that HF* relaxes via a $\mathrm{V‐V}$ transfer to N₂ with a subsequent $V\mathrm{–R–T}$ relaxation of ${\mathrm{N}}_2*$ .