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

Journal Article · Fri Jul 15 00:00:00 EDT 1994 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.467810· OSTI ID:7107515

Lanzisera, D V; Valentini, J J ^[1]

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1. Department of Chemistry, Columbia University, New York, New York 10027 (United States)

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 the positive ([ital v][prime],[ital j][prime]) correlation may be intrinsic to polyatomic hydrogen atom abstraction reactions.

• OSTI ID: 7107515
• Journal Information: Journal of Chemical Physics; (United States), Vol. 101:2; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM COMPOUNDS
DISTRIBUTION
HYDROFLUORIC ACID
HYDROGEN
CHEMICAL REACTIONS
METHYL CHLORIDE
ATOM-MOLECULE COLLISIONS
EXCITED STATES
POLYATOMIC MOLECULES
QUANTUM MECHANICS
TOTAL CROSS SECTIONS
VIBRATIONAL STATES
YIELDS
ATOM COLLISIONS
CHLORINATED ALIPHATIC HYDROCARBONS
COLLISIONS
CROSS SECTIONS
ELEMENTS
ENERGY LEVELS
FLUORINE COMPOUNDS
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
MECHANICS
MOLECULE COLLISIONS
MOLECULES
NONMETALS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
400201* - Chemical & Physicochemical Properties