STATE-TO-STATE DYNAMICS OF ATOM PLUS POLYATOM REACTIONS .3. THE H-]-HD(V',J')+CCL3 REACTION(CDCL3)

We report measurement of the HD product quantum stale distributions fo r the H+CDCl3-->HD(v',j')+CCl3 reaction at a collision energy of 1.6 e V using coherent anti-Stokes-Raman scattering (CARS). We determine rel ative HD(v',j') population distributions and absolute partial and tota l cross sections. The total cross section is 0.55+/-0.10 Angstrom(2). HD products are observed in v'=0, 1, and 2, with 7% of the available e nergy in HD product vibration. As with previous light+light-heavy-->li ght-light+heavy reactions, the total energy in rotation, 15%, is also small. HD formed in v'=1 and 2 have greater fractions of rotational en ergy in relation to the energy available to them than HD in v'=0, with g(r)=[E(rot)]/(E(tot)-E(vib))=0.15, 0.20, and 0.19 for v'=0, 1, and 2 , respectively. Linear surprisal analysis shows that the excited vibra tional levels have less bias against rotational excitation than the gr ound state level, respectively, if the CCl3 fragment is regarded as st ructureless. Comparison with previous state-to-state dynamics results of kinematically similar H+HX-->H-2+X (X=Cl, Br, I) and H+HR/DR-->H-2/ HD+R (R=CD3, C2H5, C3H7) reactions indicate that the positive (v',j') correlation may be intrinsic to polyatomic hydrogen atom abstraction r eactions.