State-to-state rates for the D + H2 (v=1, J=1) → HD(V',j') + H reaction : predictions and measurements

• Published in: Science (American Association for the Advancement of Science) 1992-07, Vol.257 (5069), p.519-522
• Main Authors: NEUHAUSER, D, JUDSON, R. S, KOURI, D. J, ADELMAN, D. E, SHAFER, N. E, KLINER, D. A. V, ZARE, R. N
• Format: Article
• Language: English
• Subjects: Chemical reactions; Chemistry; Exact sciences and technology; Inorganic chemistry and origins of life; Kinetics and mechanism of reactions; Quantum chemistry
• ISSN: 0036-8075; 1095-9203
• DOI: 10.1126/science.257.5069.519

A fully quantal wavepacket approach to reactive scattering in which the best available [H.sub.3] potential energy surface was used enabled a comparison with experimentally determined rates for the D + [H.sub.2] (v = 1, j = 1) [right arrow] HD(v' = 0, 1, 2; j') + H reaction at significantly higher total energies (1.4 to 2.25 electron volts) than previously possible. The theoretical results are obtained over a sufficient range of conditions that a detailed simulation of the experiment was possible, thus making this a definitive comparison of experiment and theory. Good to excellent agreement is found for the vibrational branching ratios and for the rotational distributions within each product vibrational level. However, the calculated rotational distributions are slightly hotter than the experimentally measured ones. This small discrepancy is more marked for products for which a larger fraction of the total energy appears in translation. The most likely explanation for this behavior is that refinements are needed in the potential energy surface.