State-to-state dynamics of atom+polyatom reactions. III. The H+CDCl[sub 3][r arrow]HD([ital v][prime],[ital j][prime])+CCl[sub 3] reaction

We report measurement of the HD product quantum state distributions for the H+CDCl[sub 3][r arrow]HD([ital v][prime],[ital j][prime])+CCl[sub 3] reaction at a collision energy of 1.6 eV using coherent anti-Stokes--Raman scattering (CARS). We determine relative HD([ital v][prime],[ital j][prime]) population distributions and absolute partial and total cross sections. The total cross section is 0.55[plus minus]0.10 A[sup 2]. HD products are observed in [ital v][prime]=0, 1, and 2, with 7% of the available energy in HD product vibration. As with previous light+light--heavy[r arrow]light--light+heavy reactions, the total energy in rotation, 15%, is also small. HD formed in [ital v][prime]=1 and 2 have greater fractions of rotational energy in relation to the energy available to them than HD in [ital v][prime]=0, with [ital g][sub [ital r]]=[l angle][ital E][sub rot][r angle]/([ital E][sub tot][minus][ital E][sub vib])=0.15, 0.20, and 0.19 for [ital v][prime]=0, 1, and 2, respectively. Linear surprisal analysis shows that the excited vibrational levels have less bias against rotational excitation than the ground state level, respectively, if the CCl[sub 3] fragment is regarded as structureless. Comparison with previous state-to-state dynamics results of kinematically similar H+HX[r arrow]H[sub 2]+X (X=Cl, Br, I) and H+HR/DR[r arrow]H[sub 2]/HD+R (R=CD[sub 3], C[sub 2]H[sub 5], C[sub 3]H[sub 7]) reactions indicate that themore » positive ([ital v][prime],[ital j][prime]) correlation may be intrinsic to polyatomic hydrogen atom abstraction reactions.« less