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Classical Density Functional Theory of Polymer Fluids.

Forsman, Jan LU and Woodward, Clifford (2016) 1.
Abstract
We introduce a classical density functional (DFT) description of polymer solutions, initially focusing on systems containing flexible and monodisperse chains. The theory is used to describe excluded volume effects by utilizing the so-called “Generalized Flory-Dimer” (GFD) equation of state. We also describe efficient computational approaches to numerical solutions. We then extend our treatment to describe semiflexible polymers and polydispersity. Here, the polydispersity, in combination with the well-known Schultz-Flory-Zimm molecular weight distribution, allows a different formulation for the free energy minimization. An interesting, and perhaps counterintuitive, result is that the resulting computational effort depends on the width of... (More)
We introduce a classical density functional (DFT) description of polymer solutions, initially focusing on systems containing flexible and monodisperse chains. The theory is used to describe excluded volume effects by utilizing the so-called “Generalized Flory-Dimer” (GFD) equation of state. We also describe efficient computational approaches to numerical solutions. We then extend our treatment to describe semiflexible polymers and polydispersity. Here, the polydispersity, in combination with the well-known Schultz-Flory-Zimm molecular weight distribution, allows a different formulation for the free energy minimization. An interesting, and perhaps counterintuitive, result is that the resulting computational effort depends on the width of the molecular weight distribution, but not the average chain length. Finally, we show how the DFT can be adapted to charged oligomeric fluids displaying more complex molecular architecture. In particular, we show that the essential non-uniform structures of a model room temperature ionic liquid are accurately captured in a DFT that accounts for non-trivial bond connectivity and strongly coupled steric and electrostatic correlations. (Less)
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author
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organization
publishing date
type
Chapter in Book/Report/Conference proceeding
publication status
published
subject
host publication
Variational Methods in Molecular Modeling
volume
1
edition
1
publisher
Springer
ISBN
978-981-10-2500-6
DOI
10.1007/978-981-10-2502-0_4
language
English
LU publication?
yes
id
d7dd72be-fb66-4d1f-8e51-82e83c00553f
date added to LUP
2019-05-27 12:34:17
date last changed
2019-06-17 14:43:37
@inbook{d7dd72be-fb66-4d1f-8e51-82e83c00553f,
  abstract     = {{We introduce a classical density functional (DFT) description of polymer solutions, initially focusing on systems containing flexible and monodisperse chains. The theory is used to describe excluded volume effects by utilizing the so-called “Generalized Flory-Dimer” (GFD) equation of state. We also describe efficient computational approaches to numerical solutions. We then extend our treatment to describe semiflexible polymers and polydispersity. Here, the polydispersity, in combination with the well-known Schultz-Flory-Zimm molecular weight distribution, allows a different formulation for the free energy minimization. An interesting, and perhaps counterintuitive, result is that the resulting computational effort depends on the width of the molecular weight distribution, but not the average chain length. Finally, we show how the DFT can be adapted to charged oligomeric fluids displaying more complex molecular architecture. In particular, we show that the essential non-uniform structures of a model room temperature ionic liquid are accurately captured in a DFT that accounts for non-trivial bond connectivity and strongly coupled steric and electrostatic correlations.}},
  author       = {{Forsman, Jan and Woodward, Clifford}},
  booktitle    = {{Variational Methods in Molecular Modeling}},
  isbn         = {{978-981-10-2500-6}},
  language     = {{eng}},
  month        = {{12}},
  publisher    = {{Springer}},
  title        = {{Classical Density Functional Theory of Polymer Fluids.}},
  url          = {{http://dx.doi.org/10.1007/978-981-10-2502-0_4}},
  doi          = {{10.1007/978-981-10-2502-0_4}},
  volume       = {{1}},
  year         = {{2016}},
}