Premium
A generalized direct‐particle‐deletion scheme for the calculation of chemical potential and solubilities of small‐ and medium‐sized molecules in amorphous polymers
Author(s) -
Siegert Martin R.,
Heuchel Matthias,
Hofmann Dieter
Publication year - 2007
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20594
Subject(s) - solubility , polymer , molecule , amorphous solid , inverse , hildebrand solubility parameter , benzene , particle (ecology) , statistical physics , materials science , thermodynamics , computational chemistry , chemistry , physics , organic chemistry , mathematics , geometry , geology , oceanography
The development, validation, and first applications of a generalized version of an inverse Widom method are described. It permits the calculation of solubility coefficients for molecules as large as, e.g., benzene in all polymers for which reasonable forcefield parameters exist. Predicting the solubility is a key to the knowledge‐based design of materials utilized to solve permeability related problems. For long time, particle insertion methods, such as the Widom method, were the only way to predict solubilities from molecular models, but they, in most cases, only worked well for rather small penetrants (e.g., H 2 , O 2 , N 2 ). Therefore, a few years ago, a new particle deletion algorithm “DPD” was introduced by Boulougouris, Economou, and Theodorou to overcome this problem in principle. The related computer code was, however, only applicable to special, relatively simple model systems. As application examples for the generalized version described here, solubility calculations for nitrogen, oxygen, and benzene in poly(dimethyl siloxane) are presented. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007