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State‐to‐state dynamics of the hydrogen exchange reaction
Author(s) -
Valentini James J.,
Gerrity Daniel P.
Publication year - 1986
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550180905
Subject(s) - chemistry , photodissociation , atomic physics , translational energy , ab initio , potential energy surface , quantum , potential energy , spectral line , hydrogen , excited state , physics , quantum mechanics , photochemistry , organic chemistry
Nascent product quantum state distributions have been measured for reactive, H + D 2 → HD + D, and inelastic, H + D 2 → D 2 ‡ + H, collisions of H with D 2 , at collision energies of 0.98 eV, 1.1 eV, and 1.3 eV. These distributions are extracted from coherent anti‐Stokes Raman scattering (CARS) spectra of HD and D 2 (recorded under single‐collision conditions) following laser photodissociation of HI to generate translationally hot H atoms in a D 2 /HI gas mixture. Variation of the photolysis wavelength allows selection of the H atom translational energy. These rotational and vibrational state distributions are compared with those obtained from quasiclassical trajectory calculations on an ab initio potential energy surface. The agreement between the calculated and measured distributions is extremely good. TheHD and D 2 product quantum state distributions are well represented by simple linear surprisal functions, with large positive vibrational and rotational surprisal.