Model calculations of isotope effects. VI. The structure of the transition state for hydrogen atom transfer from ethane to methyl radicals

Autor:	DJ McLennan
Rok vydání:	1982
Předmět:	Chemistry Ab initio quantum chemistry methods Intramolecular force Kinetic isotope effect Intermolecular force Ab initio Physical chemistry Density functional theory General Chemistry Hydrogen atom Physics::Chemical Physics Bond order
Zdroj:	Australian Journal of Chemistry. 35:1045
ISSN:	0004-9425
DOI:	10.1071/ch9821045
Popis:	Kinetic hydrogen isotope effects for the reaction C2H6 + CDB → C2H5 + CHD3 have been calculated for a large number of transition state models, bond orders being based on an ab initio structure for the ethyl radical. Various empirical relationships for transition state force fields in terms of partial bond orders were examined for each model structure. No transition state model reproduced the experimental intermolecular and intramolecular isotope effects over the temperature range, but when an Eckart tunnel correction was applied a single model gave satisfactory agreement.
Databáze:	OpenAIRE
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