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Exact density functional theory for ideal polymer fluids with nearest neighbor bonding constraints

Woodward, C. E. and Forsman, Jan LU (2008) In Journal of Chemical Physics 129(5).
Abstract
We present a new density functional theory of ideal polymer fluids, assuming nearest-neighbor bonding constraints. The free energy functional is expressed in terms of end site densities of chain segments and thus has a simpler mathematical structure than previously used expressions using multipoint distributions. This work is based on a formalism proposed by Tripathi and Chapman [Phys. Rev. Lett. 94, 087801 (2005)]. Those authors obtain an approximate free energy functional for ideal polymers in terms of monomer site densities. Calculations on both repulsive and attractive surfaces show that their theory is reasonably accurate in some cases, but does differ significantly from the exact result for longer polymers with attractive surfaces.... (More)
We present a new density functional theory of ideal polymer fluids, assuming nearest-neighbor bonding constraints. The free energy functional is expressed in terms of end site densities of chain segments and thus has a simpler mathematical structure than previously used expressions using multipoint distributions. This work is based on a formalism proposed by Tripathi and Chapman [Phys. Rev. Lett. 94, 087801 (2005)]. Those authors obtain an approximate free energy functional for ideal polymers in terms of monomer site densities. Calculations on both repulsive and attractive surfaces show that their theory is reasonably accurate in some cases, but does differ significantly from the exact result for longer polymers with attractive surfaces. We suggest that segment end site densities, rather than monomer site densities, are the preferred choice of "site functions" for expressing the free energy functional of polymer fluids. We illustrate the application of our theory to derive an expression for the free energy of an ideal fluid of infinitely long polymers. (C) 2008 American Institute of Physics. (Less)
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organization
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Contribution to journal
publication status
published
subject
keywords
POLYATOMIC FLUIDS, SURFACE FORCES, DIRECTIONAL ATTRACTIVE FORCES, LAYERS, MOLECULES, SLITLIKE PORES
in
Journal of Chemical Physics
volume
129
issue
5
publisher
American Institute of Physics
external identifiers
  • wos:000258336100039
  • scopus:49349097857
ISSN
0021-9606
DOI
10.1063/1.2957491
language
English
LU publication?
yes
id
847820c6-c1f3-4147-ba02-83c27caca6a9 (old id 1418233)
date added to LUP
2009-06-10 16:07:30
date last changed
2017-01-01 04:55:34
@article{847820c6-c1f3-4147-ba02-83c27caca6a9,
  abstract     = {We present a new density functional theory of ideal polymer fluids, assuming nearest-neighbor bonding constraints. The free energy functional is expressed in terms of end site densities of chain segments and thus has a simpler mathematical structure than previously used expressions using multipoint distributions. This work is based on a formalism proposed by Tripathi and Chapman [Phys. Rev. Lett. 94, 087801 (2005)]. Those authors obtain an approximate free energy functional for ideal polymers in terms of monomer site densities. Calculations on both repulsive and attractive surfaces show that their theory is reasonably accurate in some cases, but does differ significantly from the exact result for longer polymers with attractive surfaces. We suggest that segment end site densities, rather than monomer site densities, are the preferred choice of "site functions" for expressing the free energy functional of polymer fluids. We illustrate the application of our theory to derive an expression for the free energy of an ideal fluid of infinitely long polymers. (C) 2008 American Institute of Physics.},
  articleno    = {054902},
  author       = {Woodward, C. E. and Forsman, Jan},
  issn         = {0021-9606},
  keyword      = {POLYATOMIC FLUIDS,SURFACE FORCES,DIRECTIONAL ATTRACTIVE FORCES,LAYERS,MOLECULES,SLITLIKE PORES},
  language     = {eng},
  number       = {5},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Exact density functional theory for ideal polymer fluids with nearest neighbor bonding constraints},
  url          = {http://dx.doi.org/10.1063/1.2957491},
  volume       = {129},
  year         = {2008},
}