Advanced

Structural Anisotropy in Polar Fluids Subjected to Periodic Boundary Conditions

Stenhammar, Joakim LU ; Karlström, Gunnar LU and Linse, Per LU (2011) In Journal of Chemical Theory and Computation 7(12). p.4165-4174
Abstract (Swedish)
Abstract in Undetermined

A heuristic model based on dielectric continuum theory for the long-range solvation free energy of a dipolar system possessing periodic boundary conditions (PBCs) is presented. The predictions of the model are compared to simulation results for Stockmayer fluids simulated using three different cell geometries. The boundary effects induced by the PBCs are shown to lead to anisotropies in the apparent dielectric constant and the long-range solvation free energy of as much as 50%. However, the sum of all of the anisotropic energy contributions yields a value that is very close to the isotropic one derived from dielectric continuum theory, leading to a total system energy close to the dielectric value.... (More)
Abstract in Undetermined

A heuristic model based on dielectric continuum theory for the long-range solvation free energy of a dipolar system possessing periodic boundary conditions (PBCs) is presented. The predictions of the model are compared to simulation results for Stockmayer fluids simulated using three different cell geometries. The boundary effects induced by the PBCs are shown to lead to anisotropies in the apparent dielectric constant and the long-range solvation free energy of as much as 50%. However, the sum of all of the anisotropic energy contributions yields a value that is very close to the isotropic one derived from dielectric continuum theory, leading to a total system energy close to the dielectric value. It is finally shown that the leading-order contribution to the energetic and structural anisotropy is significantly smaller in the noncubic simulation cell geometries compared to when using a cubic simulation cell. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
7
issue
12
pages
4165 - 4174
publisher
The American Chemical Society
external identifiers
  • wos:000298118000031
  • scopus:83455260662
ISSN
1549-9618
DOI
10.1021/ct200592k
language
English
LU publication?
yes
id
49138963-9957-4353-ae2e-015fdedda85e (old id 2302919)
date added to LUP
2012-01-31 16:01:50
date last changed
2017-09-10 03:20:39
@article{49138963-9957-4353-ae2e-015fdedda85e,
  abstract     = {<b>Abstract in Undetermined</b><br/><br>
A heuristic model based on dielectric continuum theory for the long-range solvation free energy of a dipolar system possessing periodic boundary conditions (PBCs) is presented. The predictions of the model are compared to simulation results for Stockmayer fluids simulated using three different cell geometries. The boundary effects induced by the PBCs are shown to lead to anisotropies in the apparent dielectric constant and the long-range solvation free energy of as much as 50%. However, the sum of all of the anisotropic energy contributions yields a value that is very close to the isotropic one derived from dielectric continuum theory, leading to a total system energy close to the dielectric value. It is finally shown that the leading-order contribution to the energetic and structural anisotropy is significantly smaller in the noncubic simulation cell geometries compared to when using a cubic simulation cell.},
  author       = {Stenhammar, Joakim and Karlström, Gunnar and Linse, Per},
  issn         = {1549-9618},
  language     = {eng},
  number       = {12},
  pages        = {4165--4174},
  publisher    = {The American Chemical Society},
  series       = {Journal of Chemical Theory and Computation},
  title        = {Structural Anisotropy in Polar Fluids Subjected to Periodic Boundary Conditions},
  url          = {http://dx.doi.org/10.1021/ct200592k},
  volume       = {7},
  year         = {2011},
}