Potential energy surfaces kinetic isotope effect studies

Kinetic isotopic effect studies of this kind permit a test of the mass dependence predicted by transition state theory or other theories of bimolecular rate coefficients. A qualitative test of various potential energy surfaces can also be made using such data. Using the theory of Bigeleisen and Wolfsberg of kinetic isotopic effects and several methods of constructing potential energy surfaces (Wheeler et al, Sato, Johnston and Parr ) Timmons and Weston ° found no surface which predicted rates to within better than 40 % of the measured values taken as a whole. 

Chakraborty A, Zhao Y, Lin H, Tiuhlm DG (2006) Combined valence bond-molecular mechanics potential-energy surface tmd direct dynamics study of rate constants and kinetic isotope effects for the H + C2H6 reaction. J Chem Phys 124 044315... 

The isotopes of hydrogen have been used extensively in the study of kinetic isotope effects.17 A theoretical discussion from first principles of such isotope effects requires accurate potential energy surfaces for the calculation of energies and frequencies. Moreover, for the isotopes of hydrogen both tunneling and trans-... 

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