Dv. Lanzisera et Jj. Valentini, STATE-TO-STATE DYNAMICS OF ATOM PLUS POLYATOM REACTIONS .3. THE H-]-HD(V',J')+CCL3 REACTION(CDCL3), The Journal of chemical physics, 101(2), 1994, pp. 1165-1171
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.