Energy landscape design principle for optimal energy harnessing by catalytic molecular machines

Nonequilibrium Theoretical Framework and Universal Design Principles of Oscillation-Driven Catalysis

“…One can verify the result by applying it to design the catalytic inversion of spontaneous reaction under rapid temperature oscillation, where the general principle reduces to the result obtained in our previous work. 41 Examples. The universal design criterion [ ] f can guide the design of oscillation-driven catalysts with desired performance f. For illustrative purposes, this paper exemplifies the design of two interesting anomalous behaviors: (1) oscillation-induced inversion of spontaneous reaction direction and (2) oscillation-enhanced high turnover frequency without utilizing low activation barriers as required by the traditional theory.…”

“…This work significantly expands the scope of our previous work on temperature-oscillation-induced catalytic inversion. 41 This Letter provides a universal design principle of oscillationpumped anomalous performances. Furthermore, this Letter introduces a novel control-conjugate landscape description of catalytic reactions, where the reaction rate's dependence on an arbitrary environmental parameter is expressed by exponential forms that resemble the celebrated Arrhenius law.…”

“…A special case of catalytic thermal engines under temperature oscillation is demonstrated in reference. 41 Example 2: Enhancing Reaction TOF (Current). Here we illustrate the design principle for optimal enhancement of reaction current J, which is equivalent to the turnover frequency (TOF).…”

“…Additionally, the theory can be applied to the rapid oscillation of an arbitrary environmental parameter, including but not limited to temperature, electric field, pressure, and light intensity, etc. This work significantly expands the scope of our previous work on temperature-oscillation-induced catalytic inversion …”

“…In this rapid oscillation limit, the catalyst reaches a pseudostationary state, − which can be solved for as the effective steady state of the effective reaction rates. Here the effective reaction rates are the reaction rates averaged over one oscillation period boldr eff = 1 τ ∫ t 0 t 0 + τ boldr ( λ false( t false) ) .25em normald t = prefix∫ ρ ( λ ) boldr ( λ ) .25em normald λ and the time density of λ within the period is denoted by ρ(λ).…”