Development and application of advanced Monte Carlo techniques for the study of adsorption-related processes in zeolites

Zeolites are crystalline microporous materials that are used widely as industrial catalysts and adsorbents. Shape selective catalytic and adsorption properties arise because of the intimate interactions between the walls of the zeolite micropores and molecules adsorbed therein. In order to fully understand the mechanisms of adsorption and reaction in zeolites, it is necessary to examine the behavior of the adsorbed species at the molecular level. Molecular modeling is ideally suited for this task.; Configurational-bias grand canonical Monte Carlo (CB-GCMC) has been previously employed to study adsorption in zeolites for simplistic united atom (UA) sorbate models, but the methodology precluded the use of more detailed all-atom (AA) models. In the initial phase of this research, novel simulation methodologies are introduced which allow the efficient simulation of either type of model. In addition, a comprehensive software package has been developed which allows for the simulation of sorbate molecules in a wide range of microporous hosts.; The second phase of this research involved the application of the new computational tools to problems in zeolite science. Pure component and binary hydrocarbon adsorption studies were carried out in the zeolite MFI to validate the software and methodology by comparison with experiment, as well as to investigate the adsorption effects of chain length, branching, and model type. In the zeolite MOR, the adsorption of argon and light hydrocarbons was examined. The MOR studies focused on the adsorption effects of small variations in zeolite structure, lattice cations, electrostatics, and temperature. As MOR contains two distinct adsorption sites, non-ideality was detected in the mixture adsorption studies.; Finally, a study concerning zeolite catalyzed reactions was undertaken. The Constraint Index (CI) reaction was investigated through the use of a classical molecular mechanics and transition state theory (TST) framework. The TST model was evaluated through the use of Monte Carlo integration employing the new simulation methodology. Within the TST framework, the effects of reaction mechanism and temperature on observed selectivity were investigated. The results compared favorably with experiment, indicating the potential to employ classical modeling in future reaction studies.