RISM-SCF study for the rated constant of S(N)2 reaction CH3Cl+Cl- in aqueous solution

A method is proposed to evaluate the Grote-Hynes transmission coefficient b ased on the reference interaction site model self-consistent field (RISM-SC F) electronic structure calculations of reacting solute molecules combined with molecular dynamics simulation calculations of bulk solvent. The time d ependent solvent friction acting on the reaction coordinate mode is derived using the linear response approximation. An application of the present met hod is made to the S(N)2 reaction CH3Cl + Cl- in aqueous solution. The tran smission coefficient is calculated to be 0.71, which is consistent with the previous simulation studies. (C) 2001 Elsevier Science B.V. All rights res erved.