title: Computing the Heat of Adsorption using Molecular Simulations: The Effect of Strong Coulombic Interactions.
abstract: Molecular simulations are an important tool for the study of adsorption of hydrocarbons in nanoporous materials such as zeolites. The heat of adsorption is an important thermodynamic quantity that can be measured both in experiments and molecular simulations, and therefore it is often used to investigate the quality of a force field for a certain guest-host (g - h) system. In molecular simulations, the heat of adsorption in zeolites is often computed using either of the following methods: (1) using the Clausius-Clapeyron equation, which requires the partial derivative of the pressure with respect to temperature at constant loading, (2) using the energy difference between the host with and without a single guest molecule present, and (3) from energy/particle fluctuations in the grand-canonical ensemble. To calculate the heat of adsorption from experiments (besides direct calorimetry), only the first method is usually applicable. Although the computation of the heat of adsorption is straightforward for all-silica zeolites, severe difficulties arise when applying the conventional methods to systems with nonframework cations present. The reason for this is that these nonframework cations have very strong Coulombic interactions with the zeolite. We will present an alternative method based on biased interactions of guest molecules that suffers less from these difficulties. This method requires only a single simulation of the host structure. In addition, we will review some of the other important issues concerning the handling of these strong Coulombic interactions in simulating the adsorption of guest molecules. It turns out that the recently proposed Wolf method ( J. Chem. Phys. 1999, 110 , 8254 ) performs poorly for zeolites as a large cutoff radius is needed for convergence.
authors.affiliation: Process & Energy Laboratory, Delft University of Technology, Leeghwaterstraat 44, 2628CA Delft, The Netherlands, Department of Physical, Chemical, and Natural Systems, University Pablo de Olavide, Ctra. Utrera km 1, 41013 Sevilla, Spain, Chemical and Biological Engineering Department, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, and Condensed Matter and Interfaces, Utrecht University, P.O. Box 80000, 08 TA Utrecht, The Netherlands.
authors.forename: T J H
authors.initials: TJ
authors.lastname: Vlugt
authors.affiliation: Process & Energy Laboratory, Delft University of Technology, Leeghwaterstraat 44, 2628CA Delft, The Netherlands, Department of Physical, Chemical, and Natural Systems, University Pablo de Olavide, Ctra. Utrera km 1, 41013 Sevilla, Spain, Chemical and Biological Engineering Department, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, and Condensed Matter and Interfaces, Utrecht University, P.O. Box 80000, 08 TA Utrecht, The Netherlands.
authors.forename: E
authors.initials: E
authors.lastname: García-Pérez
authors.affiliation: Process & Energy Laboratory, Delft University of Technology, Leeghwaterstraat 44, 2628CA Delft, The Netherlands, Department of Physical, Chemical, and Natural Systems, University Pablo de Olavide, Ctra. Utrera km 1, 41013 Sevilla, Spain, Chemical and Biological Engineering Department, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, and Condensed Matter and Interfaces, Utrecht University, P.O. Box 80000, 08 TA Utrecht, The Netherlands.
authors.forename: D
authors.initials: D
authors.lastname: Dubbeldam
authors.affiliation: Process & Energy Laboratory, Delft University of Technology, Leeghwaterstraat 44, 2628CA Delft, The Netherlands, Department of Physical, Chemical, and Natural Systems, University Pablo de Olavide, Ctra. Utrera km 1, 41013 Sevilla, Spain, Chemical and Biological Engineering Department, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, and Condensed Matter and Interfaces, Utrecht University, P.O. Box 80000, 08 TA Utrecht, The Netherlands.
authors.forename: S
authors.initials: S
authors.lastname: Ban
authors.affiliation: Process & Energy Laboratory, Delft University of Technology, Leeghwaterstraat 44, 2628CA Delft, The Netherlands, Department of Physical, Chemical, and Natural Systems, University Pablo de Olavide, Ctra. Utrera km 1, 41013 Sevilla, Spain, Chemical and Biological Engineering Department, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, and Condensed Matter and Interfaces, Utrecht University, P.O. Box 80000, 08 TA Utrecht, The Netherlands.
authors.forename: S
authors.initials: S
authors.lastname: Calero