Abstract
Inhibited passing of reactant and product molecules within the linear pores of nanoporous catalytic materials strongly reduces reactivity. The dependence of the passing propensity on pore radius is analyzed utilizing Langevin dynamics to account for solvent effects. We find that , where passing is sterically blocked for , with below the transition state theory value. Deeper insight comes from analysis of the corresponding high-dimensional Fokker-Planck equation, which facilitates an effective small- approximation, and dimensional reduction enabling utilization of conformal mapping ideas. We analyze passing for spherical molecules and also assess the effect of rotational degrees of freedom for elongated molecules.
- Received 10 May 2014
DOI:https://doi.org/10.1103/PhysRevLett.113.038301
© 2014 American Physical Society