The effect of force on thermodynamics and kinetics of single molecule reactions.

The usual variables chemists use to affect a chemical reaction are temperature and pressure. We consider here an additional variable: force, F. By attaching a molecule to the tip of a cantilever of an atomic force microscope, or to a bead in a laser light trap, we can control the force on a single molecule. This mechanical force can drive a reaction to completion, or stabilize the reactants. Force changes the thermodynamic stability of a molecule; it can thus increase or decrease the free energy change for the reaction. Force can also speed or slow rates of reactions; it changes the free energy of activation of the reaction. Copyright 2002 Elsevier Science B.V.