Molecular-Level Simulations of Chemical Reaction Equilibrium and Diffusion in Slit and Cylindrical Nanopores: Model Dimerisation Reactions

0398865 - ÚCHP 2014 RIV GB eng J - Journal Article
Lísal, Martin - Předota, Milan - Brennan, J.K.
Molecular-Level Simulations of Chemical Reaction Equilibrium and Diffusion in Slit and Cylindrical Nanopores: Model Dimerisation Reactions.
Molecular Simulation. Roč. 39, č. 13 (2013), s. 1103-1120. ISSN 0892-7022. E-ISSN 1029-0435
R&D Projects: GA ČR GA13-09914S
Grant - others:GA ČR(CZ) GA13-08651S
Institutional support: RVO:67985858
Keywords : molecular dynamics * reaction ensemble Monte Carlo * slit and cylindrical nanopores
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 1.119, year: 2013

A molecular-level simulation study of the effects of confinement on chemical reaction equilibrium and diffusion in both slit and cylindrical nanopores is presented. First, the reaction ensemble Monte Carlo (RxMC) method is implemented to investigate the effects of nanopore size and geometry, and bulk pressure on the model dimerisation reaction, 2AOB, in slit and cylindrical nanopores in equilibrium with a vapour-phase reservoir. After determining the reaction equilibrium concentrations in the nanopore phase from RxMC simulations, canonical molecular dynamics (MD) is implemented to study the diffusion of fluid mixtures with concentrations matching the final average concentrations from the RxMC simulations. The canonical MD imulations mimic a diffusion-limited reacting system, where it is assumed that the reaction rates are very fast relative to the diffusion, and therefore assumed that chemical equilibrium is effectively maintained and unperturbed at all times in the system. The diffusion is analysed in terms of the overall and space-dependent mean-square displacement and corresponding self-diffusion coefficients.
Permanent Link: http://hdl.handle.net/11104/0226280