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We present an escape rate theory for current-induced chemical reactions. Weuse Keldysh nonequilibrium Green's functions to derive a Langevin equation forthe reaction coordinate. Due to the out of equilibrium electronic degrees offreedom, the friction, noise, and effective temperature in the Langevinequation depend locally on the reaction coordinate. As an example, we considerthe dissociation of diatomic molecules induced by the electronic current from ascanning tunnelling microscope tip. In the resonant tunnelling regime, themolecular dissociation involves two processes which are intricatelyinterconnected: a modification of the potential energy barrier and heating ofthe molecule. The decrease of the molecular barrier (i.e. the current inducedcatalytic reduction of the barrier) accompanied by the appearance of theeffective, reaction-coordinate-dependent temperature is an alternativemechanism for current-induced chemical reactions, which is distinctly differentfrom the usual paradigm of pumping vibrational degrees of freedom.

Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents