Vibrational relaxation of highly excited diatomics. II.HCl(vles;7)+20quenchers

摘要

120 vibrational relaxation rate constantskv,vminus;1Qare measured at 298 K for HCl(vles;7)collisions with six diatomics:N2,CO, NO, HCl, DCl, and HF; three triatomics:CO2,N2O,NO2;and eleven polyatomics:CH4,C2H6,C3H8,isohyphen;C4H10,CH3Cl,CH3F,CF4,SF6,CF3Cl,CF2Cl2,andCFCl3.For most quenchers,kQincreases with increasingvindependent of whether the vibrational energy gap is reduced or increased. Large collisional relaxation probabilities for highv, of order 0.1 to 1 gas kinetic, are encountered for 11 of 20 quenchers. ForQ=HC1thinsp;(v=0),the relaxation is shown experimentally to be mainlyVndash;R,Tfor highv. The rates reflect a mix of effects due to dipole and dispersion interactions, energy gap, rotation, and complex formation, and present interesting problems of interpretation.