In lattice models, local pressure on a surface is derived from the change in the free energy of the system due to the exclusion of a certain boundary site, while the total force on the surface can be obtained by a similar exclusion of all surface sites. In these definitions, while the total force on the surface of a lattice system matches the force measured in a continuous system, the local pressure does not. Moreover, in a lattice system, the sum of the local pressures is not equal to the total force as is required in a continuous system. The difference is caused by correlation between occupations of surface sites as well as finite displacement of surface elements used in the definition of the pressures and the force. This problem is particularly acute in the studies of entropic pressure of polymers represented by random or self-avoiding walks on a lattice. We propose a modified expression for the local pressure which satisfies the proper relation between the pressure and the total force, and show that for a single ideal polymer in the presence of scale-invariant boundaries it produces quantitatively correct values for continuous systems. The required correction to the pressure is non-local, i.e., it depends on long range correlations between contact points of the polymer and the surface.
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28 November 2014
Research Article|
November 26 2014
Entropic pressure in lattice models for polymers
Yosi Hammer;
Yosi Hammer
a)
Raymond and Beverly Sackler School of Physics and Astronomy,
Tel Aviv University
, Tel Aviv 69978, Israel
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Yacov Kantor
Yacov Kantor
Raymond and Beverly Sackler School of Physics and Astronomy,
Tel Aviv University
, Tel Aviv 69978, Israel
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a)
Electronic mail: hammeryosi@gmail.com
J. Chem. Phys. 141, 204905 (2014)
Article history
Received:
October 06 2014
Accepted:
November 10 2014
Citation
Yosi Hammer, Yacov Kantor; Entropic pressure in lattice models for polymers. J. Chem. Phys. 28 November 2014; 141 (20): 204905. https://doi.org/10.1063/1.4902231
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