Perturbation Theory versus Thermodynamic Integration. Beyond a Mean-Field Treatment of Pair Correlations in a Nematic Model Liquid Crystal.
File(s)manuscript.pdf (12.67 MB)
Accepted version
Author(s)
Schoen, M
Haslam, AJ
Jackson, G
Type
Journal Article
Abstract
The phase behavior and structure of a simple square-well bulk fluid with anisotropic interactions is described in detail. The orientation dependence of the intermolecular interactions allows for the formation of a nematic liquid-crystalline phase in addition to the more conventional isotropic gas and liquid phases. A version of classical density functional theory (DFT) is employed to determine the properties of the model, and comparisons are made with the corresponding data from Monte Carlo (MC) computer simulations in both the grand canonical and canonical ensembles, providing a benchmark to assess the adequacy of the DFT results. A novel element of the DFT approach is the assumption that the structure of the fluid is dominated by intermolecular interactions in the isotropic fluid. A so-called augmented modified mean-field (AMMF) approximation is employed accounting for the influence of anisotropic interactions. The AMMF approximation becomes exact in the limit of vanishing density. We discuss advantages and disadvantages of the AMMF approximation with respect to an accurate description of isotropic and nematic branches of the phase diagram, the degree of orientational order, and orientation-dependent pair correlations. The performance of the AMMF approximations is found to be good in comparison with the MC data; the AMMF approximation has clear advantages with respect to an accurate and more detailed description of the fluid structure. Possible strategies to improve the DFT are discussed.
Date Issued
2017-08-03
Date Acceptance
2017-08-02
Citation
Langmuir, 2017, 33 (42), pp.11345-11365
ISSN
0743-7463
Publisher
American Chemical Society
Start Page
11345
End Page
11365
Journal / Book Title
Langmuir
Volume
33
Issue
42
Copyright Statement
© 2017 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Langmuir, after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.langmuir.7b01849
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/28772076
Subjects
MD Multidisciplinary
Chemical Physics
Publication Status
Published
Coverage Spatial
United States