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Investigation of the dynamics of benzene in silicalite using transition-state theory ion-state

Journal Article · · Journal of Physical Chemistry; (United States)
DOI:https://doi.org/10.1021/j100097a022· OSTI ID:6602179
; ;  [1]
  1. Univ. of California, Berkeley, CA (United States) Lawrence Berkeley Lab., CA (United States)

The dynamics of benzene in silicalite at low loading was investigated using transition-state theory. Benzene was found to diffuse by infrequent hops between preferred adsorption sites. Potential energy minima and saddle points were located using an atomistic model, and diffusion paths connecting pairs of minima were constructed through each saddle point (transition state). The intrinsic reaction coordinate (IRC) approach was used to construct the diffusion paths in six dimensions. The IRC equations are presented for the motion of a rigid body (benzene) through a static potential field (silicalite). A rate constant for each transition between minima was calculated using a harmonic approximation to the potential energy function. From the rate constants, the self-diffusivity was computed with a dynamic Monte Carlo simulation. An activation energy of 36.7 kJ/mol was calculated. This is larger than the experimental value, and the predicted diffusivities are 1-2 orders of magnitude smaller than experiment. 51 refs., 7 figs., 3 tabs.

DOE Contract Number:
AC03-76SF00098
OSTI ID:
6602179
Journal Information:
Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 98:46; ISSN JPCHAX; ISSN 0022-3654
Country of Publication:
United States
Language:
English