  Confined nanoscale spaces, electric fields and tunneling currents make the
molecular electronic junction an experimental device for the discovery of new,
out-of-equilibrium chemical reactions. Reaction-rate theory for
current-activated chemical reactions is developed by combining a Keldysh
nonequilibrium Green's functions treatment of electrons, Fokker-Planck
description of the reaction coordinate, and Kramers' first-passage time
calculations. The NEGF provide an adiabatic potential as well as a diffusion
coefficient and temperature with local dependence on the reaction coordinate.
Van Kampen's Fokker-Planck equation, which describes a Brownian particle moving
in an external potential in an inhomogeneous medium with a position-dependent
friction and diffusion coefficient, is used to obtain an analytic expression
for the first-passage time. The theory is applied to several transport
scenarios: a molecular junction with a single, reaction coordinate dependent
molecular orbital, and a model diatomic molecular junction. We demonstrate the
natural emergence of Landauer's blowtorch effect as a result of the interplay
between the configuration dependent viscosity and diffusion coefficients. The
resultant localized heating in conjunction with the bond-deformation due to
current-induced forces are shown to be the determining factors when considering
chemical reaction rates; each of which result from highly tunable parameters
within the system.
