Weighted density approximation for bonding in molecules: ring and cage polymers

M B Sweatman

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The focus of this work is the bonded contribution to the intrinsic Helmholtz free energy of molecules. A weighted density approximation (WDA) for this contribution is presented within the interaction site model (ISM) for ring and cage polymers. The resulting density functional theory (ISM/WDA) for these systems is no more complex than theories for a pure simple fluid, and much less complex than density functional approaches that treat the bonding functional exactly. The ISM/WDA bonding functional is much more accurate than either the ISM/HNC or ISM/PY bonding functionals, which are related to the reference interaction-site model (RISM)/HNC and RISM/PY integral equations respectively, for ideal ring polymers. This means that the ISM/WDA functional should generally be more accurate for most 'real' ring or cage polymer systems when any reasonable approximation for the 'excess' contribution to the intrinsic Helmholtz free energy is employed.
LanguageEnglish
Pages3875-3890
Number of pages15
JournalJournal of Physics: Condensed Matter
Volume15
Issue number23
DOIs
Publication statusPublished - 18 Jun 2003

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Polymers
Molecules
rings
polymers
approximation
molecules
interactions
Free energy
free energy
functionals
Integral equations
Density functional theory
integral equations
density functional theory
Fluids
fluids

Keywords

  • weighted density
  • bonding molecules
  • ring polymers
  • cage polymers
  • condensed matter

Cite this

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Weighted density approximation for bonding in molecules : ring and cage polymers. / Sweatman, M B.

In: Journal of Physics: Condensed Matter, Vol. 15, No. 23, 18.06.2003, p. 3875-3890.

Research output: Contribution to journalArticle

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AB - The focus of this work is the bonded contribution to the intrinsic Helmholtz free energy of molecules. A weighted density approximation (WDA) for this contribution is presented within the interaction site model (ISM) for ring and cage polymers. The resulting density functional theory (ISM/WDA) for these systems is no more complex than theories for a pure simple fluid, and much less complex than density functional approaches that treat the bonding functional exactly. The ISM/WDA bonding functional is much more accurate than either the ISM/HNC or ISM/PY bonding functionals, which are related to the reference interaction-site model (RISM)/HNC and RISM/PY integral equations respectively, for ideal ring polymers. This means that the ISM/WDA functional should generally be more accurate for most 'real' ring or cage polymer systems when any reasonable approximation for the 'excess' contribution to the intrinsic Helmholtz free energy is employed.

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KW - cage polymers

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