Chemiluminescence-depletion of vibrational relaxation. Part 1.—HF(v= 2–6)+ CO2, DF(v= 2–4)+ CO2

Abstract

The chemiluminescence depletion (C.D.) method has been used to obtain the relative rate of vibrational relaxation of HF (v= 2–6) and DF (v= 2–4) in collisions with CO₂. In both cases the rate constant k(v→v–1) increases approximately linearly with v over the range from v= 1 up to the stated limit of observation. The C.D. method is at present unique in permitting a rough measurement to be made of the variation of vibrational relaxation rate constant with rotational quantum number, J. This more-detailed relaxation rate constant, k(v, J→v–1), shows an initial decrease in vibrational transfer efficiency as J increases from J= 0 to J≈ 6.