Shen, V.
and Siderius, D.
(2014),
Elucidating the Effects of Adsorbent Flexibility on Fluid Adsorption Using Simple Models and Flat-Histogram Sampling Methods, Journal of Chemical Physics, [online], https://doi.org/10.1063/1.4884124 (Accessed May 10, 2026)
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
Secure .gov websites use HTTPS
A lock (
) or https:// means you’ve safely connected to the .gov website. Share sensitive information only on official, secure websites.
Elucidating the Effects of Adsorbent Flexibility on Fluid Adsorption Using Simple Models and Flat-Histogram Sampling Methods
Published
Author(s)
,
Abstract
Using flat-histogram Monte Carlo methods, we investigate the adsorptive behavior of the square-well fluid in two simple slit-pore- like models intended to capture fundamental characteristics of flexible adsorbent materials. The models require thermodynamic information about the flexible adsorbent material itself as input. An important component of this work involves formulating the flexible pore models in the appropriate thermodynamic (statistical mechanical) ensembles, namely the osmotic ensemble and a variant of the grand-canonical ensemble. Two-dimensional probability distributions, which are calculated by flat-histogram methods, provide the information necessary to determine the adsorptive properties. From these distributions, we are able to determine precisely adsorption isotherms, (equilibrium) phase transition conditions, limits of stability, and free energies for a number of different flexible adsorbent materials, distinguishable as different inputs into the models. While the models used in this work are relatively simple from a geometric perspective, they yield non-trivial adsorptive behavior, including adsorption-desorption hysteresis solely due to material flexibility and so-called ``breathing" of the adsorbent. The observed effects can in turn be tied to the inherent properties of the bare adsorbent. Some of the effects are expected on physical grounds while others arise from a subtle balance of thermodynamic and mechanical driving forces. In addition, the computational strategy presented here can be easily applied to more complex models for flexible adsorbents.Citation
Journal of Chemical Physics
Volume
140
Pub Type
Journals
Download Paper
Keywords
molecular simulation, statistical mechanics, thermodynamics, adsorption
Citation
Issues
If you have any questions about this publication or are having problems accessing it, please contact [email protected].
Created June 24, 2014, Updated April 8, 2026