Modeling Solubilities of Additives in Polymer Microstructures : Single-Step Perturbation Method Based on a Soft-Cavity Reference State

Özal, Tugba A.; Peter, Christine; Hess, Berk; van der Vegt, Nico F. A.

Modeling Solubilities of Additives in Polymer Microstructures : Single-Step Perturbation Method Based on a Soft-Cavity Reference State

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Datum

2008

Autor:innen

Özal, Tugba A.

Peter, Christine

Hess, Berk

van der Vegt, Nico F. A.

DOI (zitierfähiger Link)

https://doi.org/10.1021/ma702329q

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

Macromolecules. 2008, 41(13), pp. 5055-5061. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma702329q

Zusammenfassung

Solubilities of additive molecules whose molecular sizes exceed the typical dimensions of free volume cavities pre-existing in amorphous polymer melts and glasses cannot readily be computed in molecular simulations. In this paper, we perform molecular dynamics simulations of a soft-cavity reference state ensemble, which contains a soft-core, fast diffusing, Lennard-Jones particle in a rigid-chain polymer matrix. By means of the Zwanzig thermodynamic perturbation formalism, the soft particle has been perturbed to various real-solute end-states. It is shown that with this approach it is possible to overcome some of the free energy sampling problems related to the insertion of large solutes and slow diffusion in the end-state. We have calculated the excess chemical potentials of propane, chloroform, and dimethyl sulfoxide in liquid bisphenol A−polycarbonate and show that a single simulation of the reference state is sufficient to obtain statistical accuracies within error bars of 0.5−0.8 kBT. The method is particularly useful for calculating solubility ratios of large molecular solutes with approximately equal excluded volume radii.

Fachgebiet (DDC)

540 Chemie

Zitieren

ISO 690

ÖZAL, Tugba A., Christine PETER, Berk HESS, Nico F. A. VAN DER VEGT, 2008. Modeling Solubilities of Additives in Polymer Microstructures : Single-Step Perturbation Method Based on a Soft-Cavity Reference State. In: Macromolecules. 2008, 41(13), pp. 5055-5061. ISSN 0024-9297. eISSN 1520-5835. Available under: doi: 10.1021/ma702329q

BibTex

@article{Ozal2008-07Model-40204,
  year={2008},
  doi={10.1021/ma702329q},
  title={Modeling Solubilities of Additives in Polymer Microstructures : Single-Step Perturbation Method Based on a Soft-Cavity Reference State},
  number={13},
  volume={41},
  issn={0024-9297},
  journal={Macromolecules},
  pages={5055--5061},
  author={Özal, Tugba A. and Peter, Christine and Hess, Berk and van der Vegt, Nico F. A.}
}

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