State-to-state dynamics of the hydrogen exchange reaction

✍ Scribed by James J. Valentini; Daniel P. Gerrity

• Publisher: John Wiley and Sons
• Year: 1986
• Tongue: English
• Weight: 501 KB
• Volume: 18
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550180905

✦ Synopsis

Nascent product quantum state distributions have been measured for reactive, H + D, -+ HD + D, and inelastic, H + D, ---t D,' + H, collisions of H with D2, 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, (recorded under single-collision conditions) following laser photodissociation of HI to generate translationally hot H atoms in a D2/HI gas mixture. Variation of the photolysis wavelength allows selection of the H atom translational energy. These rotational and vibrational state distributions a r e compared with those obtained from quasiclassical trajectory calculations on a n ab initio potential energy surface. The agreement between the calculated and measured distributiws is extremely good. The HD and D2 product quantum state distributions are well represented by simple linear surprisal functions, with large positive vibrational and rotational surprisal.