text: Oscillating binding energies of all surface chemical species introduces periodic instances of transient behavior to the catalytic surface. For slow oscillation frequencies, the transient period is only a small quantity of the oscillation time scale, and the surface reaction achieves a new steady state. However, as the oscillation frequency increases, the surface transient period approaches the timescale of the oscillation and the catalytic surface remains in a constant transient condition. A plot of the averaged turnover frequency of a reaction with respect to applied oscillation frequency identifies the resonant frequency range for which the transient conditions of the catalyst surface match the applied frequencies.  The resonance band exists above the Sabatier volcano plot maximum of a static system with average reaction rates as high as five orders of magnitude faster than that achievable by conventional catalysis.
  Surface binding energy oscillation also occurs to different extent with the various chemical surface species as defined by the γ parameter. For any non-unity γ system, the asymmetry in the surface energy profile results in conducting work to bias the reaction to a steady state away from equilibrium.  Similar to the controlled directionality of molecular machines, the resulting ratchet (device) energy mechanism selectively moves molecules through a catalytic reaction against a free energy gradient.
  Application of dynamic binding energy to a surface with multiple catalytic reactions exhibits complex behavior derived from the differences in the natural frequencies of each chemistry; these frequencies are identified by the inverse of the adsorption, desorption, and surface kinetic rate parameters.  Considering a system of two parallel elementary reactions of A-to-B and A-to-C that only occur on a surface, the performance of the catalyst under dynamic conditions will result in varying capability for selecting either reaction product (B or C).  For the depicted system, both reactions have the same overall thermodynamics and will produce B and C in equal amounts (50% selectivity) at chemical equilibrium.  Under normal static catalyst operation, only product B can be produced at selectivities greater than 50% and product C is never favored.  However, as shown, the application of surface binding dynamics in the form of a square wave at varying frequency and fixed oscillation amplitude but varying endpoints exhibits the full range of possible reactant selectivity.  In the range of 1-10 Hertz, there exists a small island of parameters for which product C is highly selective; this condition is only accessible via dynamics.