Langevin and Fokker-Planck Analyses of Inhibited Molecular Passing Processes Controlling Transport and Reactivity in Nanoporous Materials

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2014-07-01
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Ackerman, David
Slowing, Igor
Evans, James
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Slowing, Igor
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Evans, James
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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 P on pore radius R is analyzed utilizing Langevin dynamics to account for solvent effects. We find that P∼(R−Rc)σ, where passing is sterically blocked for R≤Rc, with σ below the transition state theory value. Deeper insight comes from analysis of the corresponding high-dimensional Fokker-Planck equation, which facilitates an effective small-P 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.

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This article is from Physical Review Letters 113 (2014): 038301, doi:10.1103/PhysRevLett.113.038301. Posted with permission.

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Wed Jan 01 00:00:00 UTC 2014
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