Chemistry, Physics and Astronomy, Ames Laboratory
Journal or Book Title
Journal of Chemical Physics
We analyze a model for polymerization at catalytic sites distributed within parallel linear pores of a mesoporous material. Polymerization occurs primarily by reaction of monomers diffusing into the pores with the ends of polymers near the pore openings. Monomers and polymers undergo single-file diffusion within the pores. Model behavior, including the polymer length distribution, is determined by kinetic Monte Carlo simulation of a suitable atomistic-level lattice model. While the polymers remain within the pore, their length distribution during growth can be described qualitatively by a Markovian rate equation treatment. However, once they become partially extruded, the distribution is shown to exhibit non-Markovian scaling behavior. This feature is attributed to the long-tail in the “return-time distribution” for the protruding end of the partially extruded polymer to return to the pore, such return being necessary for further reaction and growth. The detailed form of the scaled length distribution is elucidated by application of continuous-time random walk theory.
Copyright 2010 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.
American Institute of Physics
Liu, Da-Jiang; Chen, Hung-Ting; Lin, Victor S.-Y.; and Evans, James W., "Polymer length distributions for catalytic polymerization within mesoporous materials: Non-Markovian behavior associated with partial extrusion" (2010). Physics and Astronomy Publications. 193.