Rates of adsorption and desorption: Entropic contributions and errors due to meanfield approximations
Abstract
We have performed exact classical rate calculations to compute adsorption and desorption rate constants with a model representative of a real system. We compute the desorption rate using transitionstate theory by taking the dividingsurface far from the surface of the solid. We find that using a meanfield assumption, i.e., applying potential of mean force to transition state theory, could lead to two ordersofmagnitude errors in the rate constant owing to large fluctuations in the desorption barrier. Furthermore, we compute the adsorption rate by including a dynamical factor which reflects the probability of sticking to the solid surface. We find that the sticking probability is highly sensitive to the coverage. Also, we find that the adsorption rate computed from the meanfield assumption is not very different from the exact adsorption rate. We also compute entropic contribution to desorption rates and compare it to that obtained from two limiting models of adsorption—2D ideal gas and 2D ideal lattice gas. We show that at high temperatures (700 K), the entropic contribution to desorption rates computed from the exact calculations is very close to that obtained from the 2D ideal gas model. However, for lower to intermediate temperatures from 200 K to 500 K,more »
 Authors:

 Indian Inst. of Technology (IIT), Kanpur (India)
 Univ. of California, Santa Barbara, CA (United States). Dept. of Chemistry and Biochemistry
 Publication Date:
 Research Org.:
 Univ. of California, San Diego, CA (United States)
 Sponsoring Org.:
 USDOE Office of Science (SC)
 OSTI Identifier:
 1614579
 Alternate Identifier(s):
 OSTI ID: 1523558
 Grant/Contract Number:
 FG0389ER14048
 Resource Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 150; Journal Issue: 18; Journal ID: ISSN 00219606
 Publisher:
 American Institute of Physics (AIP)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Chemistry; Physics; Surface and interface chemistry; Adsorption; Activation energies; Transition state theory; Statistical thermodynamics; Diatomic molecule; Entropy; Reaction rate constants
Citation Formats
Agarwal, Vishal, and Metiu, Horia. Rates of adsorption and desorption: Entropic contributions and errors due to meanfield approximations. United States: N. p., 2019.
Web. doi:10.1063/1.5095867.
Agarwal, Vishal, & Metiu, Horia. Rates of adsorption and desorption: Entropic contributions and errors due to meanfield approximations. United States. doi:10.1063/1.5095867.
Agarwal, Vishal, and Metiu, Horia. Tue .
"Rates of adsorption and desorption: Entropic contributions and errors due to meanfield approximations". United States. doi:10.1063/1.5095867. https://www.osti.gov/servlets/purl/1614579.
@article{osti_1614579,
title = {Rates of adsorption and desorption: Entropic contributions and errors due to meanfield approximations},
author = {Agarwal, Vishal and Metiu, Horia},
abstractNote = {We have performed exact classical rate calculations to compute adsorption and desorption rate constants with a model representative of a real system. We compute the desorption rate using transitionstate theory by taking the dividingsurface far from the surface of the solid. We find that using a meanfield assumption, i.e., applying potential of mean force to transition state theory, could lead to two ordersofmagnitude errors in the rate constant owing to large fluctuations in the desorption barrier. Furthermore, we compute the adsorption rate by including a dynamical factor which reflects the probability of sticking to the solid surface. We find that the sticking probability is highly sensitive to the coverage. Also, we find that the adsorption rate computed from the meanfield assumption is not very different from the exact adsorption rate. We also compute entropic contribution to desorption rates and compare it to that obtained from two limiting models of adsorption—2D ideal gas and 2D ideal lattice gas. We show that at high temperatures (700 K), the entropic contribution to desorption rates computed from the exact calculations is very close to that obtained from the 2D ideal gas model. However, for lower to intermediate temperatures from 200 K to 500 K, the entropic contributions cover a wide range which lies in between the two limiting models and could lead to over twoordersofmagnitude errors in the rate coefficient.},
doi = {10.1063/1.5095867},
journal = {Journal of Chemical Physics},
number = 18,
volume = 150,
place = {United States},
year = {2019},
month = {5}
}
Web of Science
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