TY - JOUR
T1 - Force field and tunneling effects in the H-H-CL reaction system. Determination from kinetic-isotope-effect measurements
AU - Stern, Marvin J.
AU - Persky, A.
AU - Klein, F. S.
PY - 1973
Y1 - 1973
N2 - An iterative method is used to obtain, within the framework of the transition state theory, sets of force constants from experimental kinetic-isotope-effect data for the reaction system H2 -> H + HQ. Two sets of force constants, describing quite different transition-state structures, are found to be equally compatible with all available rate data for the reactions of chlorine atoms with H,, HD, HT, DT, Dj, and T,. These force fields are compared with force fields derived by semiempirical methods. Measurements of the intramolecular kinetic isotope effect, i.e., the relative rate of production of HC1/DC1 in the reaction HD+C1, are shown to be especially suited for selecting compatible transition-state models.
AB - An iterative method is used to obtain, within the framework of the transition state theory, sets of force constants from experimental kinetic-isotope-effect data for the reaction system H2 -> H + HQ. Two sets of force constants, describing quite different transition-state structures, are found to be equally compatible with all available rate data for the reactions of chlorine atoms with H,, HD, HT, DT, Dj, and T,. These force fields are compared with force fields derived by semiempirical methods. Measurements of the intramolecular kinetic isotope effect, i.e., the relative rate of production of HC1/DC1 in the reaction HD+C1, are shown to be especially suited for selecting compatible transition-state models.
UR - http://www.scopus.com/inward/record.url?scp=36849112144&partnerID=8YFLogxK
U2 - 10.1063/1.1679194
DO - 10.1063/1.1679194
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AN - SCOPUS:36849112144
SN - 0021-9606
SP - 5697
EP - 5706
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
ER -