Structural Anisotropy in Polar Fluids Subjected to Periodic Boundary Conditions
(2011) In Journal of Chemical Theory and Computation 7(12). p.4165-4174- Abstract
- 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... (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:
https://lup.lub.lu.se/record/2302919
- author
- Stenhammar, Joakim LU ; Karlström, Gunnar LU and Linse, Per LU
- organization
- publishing date
- 2011
- 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 (ACS)
- external identifiers
-
- wos:000298118000031
- scopus:83455260662
- ISSN
- 1549-9618
- DOI
- 10.1021/ct200592k
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039), Physical Chemistry 1 (S) (011001006)
- id
- 49138963-9957-4353-ae2e-015fdedda85e (old id 2302919)
- date added to LUP
- 2016-04-01 10:47:04
- date last changed
- 2023-01-02 07:46:56
@article{49138963-9957-4353-ae2e-015fdedda85e,
abstract = {{Abstract in Undetermined<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 (ACS)}},
series = {{Journal of Chemical Theory and Computation}},
title = {{Structural Anisotropy in Polar Fluids Subjected to Periodic Boundary Conditions}},
url = {{https://lup.lub.lu.se/search/files/2135361/2337098.pdf}},
doi = {{10.1021/ct200592k}},
volume = {{7}},
year = {{2011}},
}