title: Simulating the relaxation dynamics of microwave-driven zeolites.
abstract: We have performed equilibrium and nonequilibrium molecular dynamics simulations to study how microwave (MW)-heated zeolite systems relax to thermal equilibrium. We have simulated the relaxation of both ionic and dipolar phases in FAU-type zeolites, finding biexponential relaxation in all cases studied. Fast-decay times were uniformly below 1 ps, while slow-decay times were found to be as long as 14 ps. Fast-decay times increase with an increase in the initial temperature difference between MW-heated ions/dipoles and the equilibrium system. Slow-decay times were found to be relatively insensitive to the details of the MW-heated nonequilibrium state. Velocity, force, and orientational correlation functions, calculated at equilibrium to explore the natural dynamics of energy transfer, decay well before 1 ps and show little evidence of biexponential decay. In contrast, kinetic energy correlation functions show strong biexponential behavior with slow-decay times as long as 14 ps. We suggest a two-step mechanism involving initial, efficient energy transfer mediated by strongly anharmonic zeolite-guest forces, followed by a slower process mediated by weakly anharmonic couplings among normal modes of the zeolite framework. In addition to elucidating relaxation from MW-heated states, we expect that these studies will shed light on energy transfer in other contexts, such as adsorption and reaction in zeolites, which often involve significant heat release.
authors.affiliation: Department of Chemistry and Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003, USA.
authors.forename: Aldo F
authors.initials: AF
authors.lastname: Combariza
authors.forename: Ethan
authors.initials: E
authors.lastname: Sullivan
authors.forename: Scott M
authors.initials: SM
authors.lastname: Auerbach
authors.forename: Cristian
authors.initials: C
authors.lastname: Blanco