화학공학소재연구정보센터
Chemical Physics Letters, Vol.409, No.1-3, 38-42, 2005
Dual-level direct dynamics calculations of kinetic isotope effects for the CH4+F -> CH3+HF abstraction reaction
Kinetic isotope effects (KIE) for hydrogen abstraction from CH4, CD4, and (CH4)-C-13 by fluorine was studied by the variational transition state theory with multidimensional tunneling contributions (VTST/MT). A low-level potential energy surface is obtained with the AM1SRP method. High-level energies, geometries and frequencies of the reactants, transition state, and products were computed using MP2 and CCSD(T) methods. Using the CVT/mu OMT method, the kH/kD kinetic isotope effect value is 1.52 (298 K), in excellent agreement with experimental values (1.4-1.5). All computed values of k(12)C/k(13)C KIE over a large range of temperatures (200-2000 K) show normal values (KIE > 1). (c) 2005 Elsevier B.V. All rights reserved.