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On the pressure equation for chain molecules

Authors: K. G. Honnell; C. K. Hall; R. Dickman;

On the pressure equation for chain molecules

Abstract

The pressure equation is derived for fluids containing chain molecules interacting with site–site potentials. Three models are considered: a flexible chain with harmonic potentials for bond-length and bond-angle variations, a flexible chain in the limit as the force constants for the vibrations become infinite, and a chain where bond angles and lengths are rigidly constrained to their equilibrium values. In the flexible model, the pressure is found to depend on only site–site correlations and contains both inter- and intramolecular contributions. Forces arising from angular potentials, however, do not appear in the equation. In the limit as the force constants for internal vibration become infinite, the intermolecular contribution to the pressure remains a function of pair correlations, but the intramolecular term becomes a function of chain orientation and depends on three-site correlations. The result is consistent with an expression used previously for dimers and trimers, but disagrees with a site–site equation previously used to study longer chains. The equation of state for the rigidly constrained model takes the same functional form as the equation for the infinitely stiff model. However, the two-molecule correlation function appearing in the rigid equation differs from its stiff counterpart as a result of the imposed constraints.

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Powered by OpenAIRE graph
Found an issue? Give us feedback
selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
89
Top 10%
Top 1%
Top 10%
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