A quantum dynamical treatment of symmetry-induced kinetic isotope effects in the formation of He2 +

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Abstract

Kinetic isotope effects for He2 + formation are calculated quantum dynamically using high-quality Born-Oppenheimer (BO) potentials for two electronic states of He2 + and an accurate treatment of all nonadiabatic BO corrections. The two potentials are coupled only when the helium isotopes are different, and the calculations reveal that this coupling is sufficient to allow the two sets of distinguishable reactants, 4He+ + 3He or 3He + + 4He, to yield He2 + with comparable efficiency over a wide temperature range. Consequently, the potential coupling provides a significant formation rate enhancement for the low isotopic symmetry reactants, as compared to the symmetrical cases (e.g., 4He+ + 4He or 3He+ + 3He). The computed symmetry-induced kinetic isotope effects (SIKIEs) are in substantial agreement with the available experimental results and represent the first theoretical demonstration of this unusual kinetic phenomenon. Possible application of SIKIE to ozone formation and other chemical systems is discussed.

Original languageEnglish
Pages (from-to)16969-16975
Number of pages7
JournalJournal of the American Chemical Society
Volume127
Issue number48
DOIs
StatePublished - Dec 7 2005

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