Catalytic Resonance Theory: Experimental and Kinetic Interpretation of Programmable Catalysis

The complexity of programmable catalysts that change in physical or electronic state on the time scale of a catalytic turnover results in uncertainty as to the kinetic outcome of standard measurements with dynamic catalyst experiments. To provide interpretation of utility to experimentalists, a general programmable catalytic reaction exhibiting high turnover efficiency was simulated to understand the kinetic behavior of catalysts with varying frequency, binding energy oscillation amplitude, and minimum oscillation binding energy at different temperatures and reactant gas pressures. The time-averaged catalytic rate for varying temperature in the form of an Arrhenius plot exhibited three distinct kinetic regimes, with the intermediate temperatures or applied frequencies exhibiting zero slope indicative of barrier-free kinetic control. Transitions in experimentally-measurable kinetic regimes with both temperature and applied catalyst oscillation frequency were associated with transitions in sensitivity of reaction rate constants and degrees of rate control. These distinct kinetic macroscopic features specific to programmable catalysts were identified for observation in experimental dynamic kinetic measurements.