Abstract
The frictional forces exerted by a solvent are known to affect a barrier-crossing process and lead to rates in condensed phase reactions often differing significantly from predictions of transition-state theory. The proton transfer process between water molecules is studied here through a generalised Langevin equation following the Grote—Hynes result on modified Kramers' theory and its quantum generalisation by Wolynes. The Grotthuss' mechanism for the high mobility of hydrogen ions involves a proton transfer step followed by the rotation of a water molecule. The slowing down of both steps (proton transfer and rotation) by solvent friction is shown to be important as the barrier is flattened. The solvent-induced isotope effects in thermal activation as well as quantum tunneling mechanisms for both steps are shown to be significant.
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