| Abstract
| - An application of the coupled reference interaction site model (RISM)/simulation methodology to the calculationof the potential of mean force (PMF) curve in aqueous solution for the identity nucleophilic substitutionreaction Cl- + CH3Cl is performed. The free energy of activation is calculated to be 27.1 kcal/mol whichcompares very well with the experimentally determined barrier height of 26.6 kcal/mol. Furthermore, thecalculated PMF is almost superimposed with that previously calculated using the computationally rigorousMonte Carlo with importance sampling method (Chandrasekhar, J.; Smith, S. F.; Jorgensen, W. L. J. Am.Chem. Soc.1985, 107, 154). Using the calculated PMF, a crude estimate of the solvated kinetic transmissioncoefficient also compares well with that of previous more accurate simulations. These results indicate thatthe coupled RISM/simulation method provides a cost-effective methodology for studying reactions in solution.
|
