MODELING TRANSITION-STATE SOLVATION AT THE SINGLE-MOLECULE LEVEL - TEST OF CORRELATED AB-INITIO PREDICTIONS AGAINST EXPERIMENT FOR THE GAS-PHASE S(N)2 REACTION OF MICROHYDRATED FLUORIDE WITH METHYL-CHLORIDE

Extended-basis-set calculations including electron correlation have been carried out on the reactants, products, and saddle point of the gas-phase S(N)2 reaction F-(H2O) + CH3Cl and its deuterium substituted analogs. Transition state theory (TST) rate constants and secondary deuterium kinetic isotope effects (KIEs) are calculated for both CD3 and D2O substitution, and the results are in excellent agreement with recent experiments.