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Electric multipole moment fluctuations in polar liquids.

Stenhammar, Joakim LU ; Linse, Per LU ; Malmqvist, Per-Åke LU and Karlström, Gunnar LU (2009) In Journal of Chemical Physics 130(12).
Abstract
A general expression for the distribution of the fluctuating 2(l)-pole moment M(l) of a spherical sample of dielectric material is derived on the basis of dielectric theory combined with statistical mechanics. The formulas are compared with results from computer simulations of a weakly coupled Stockmayer fluid and the agreement is shown to be excellent. Furthermore, we calculate the size of the coupling, quantified through the free energy of solvation A(solv), of the fluctuating electric moments to a surrounding dielectric medium. It turns out that the contribution to A(solv) from each fluctuating electric moment actually increases with increasing order l of the moment, resulting in a formally infinite free energy of solvation. We also... (More)
A general expression for the distribution of the fluctuating 2(l)-pole moment M(l) of a spherical sample of dielectric material is derived on the basis of dielectric theory combined with statistical mechanics. The formulas are compared with results from computer simulations of a weakly coupled Stockmayer fluid and the agreement is shown to be excellent. Furthermore, we calculate the size of the coupling, quantified through the free energy of solvation A(solv), of the fluctuating electric moments to a surrounding dielectric medium. It turns out that the contribution to A(solv) from each fluctuating electric moment actually increases with increasing order l of the moment, resulting in a formally infinite free energy of solvation. We also present a correction to A(solv) for molecular media, which shows that the molecular nature of the surrounding medium effectively suppresses the divergence in the solvation free energy. (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 Physics
volume
130
issue
12
publisher
American Institute of Physics
external identifiers
  • wos:000264775200067
  • pmid:19334865
  • scopus:63649098966
ISSN
0021-9606
DOI
10.1063/1.3100312
language
English
LU publication?
yes
id
cf3cd297-ec9c-413d-ac83-7948e92353d5 (old id 1392571)
alternative location
http://jcp.aip.org/resource/1/jcpsa6/v130/i12/p124521_s1
date added to LUP
2009-05-06 13:15:19
date last changed
2017-07-30 03:31:40
@article{cf3cd297-ec9c-413d-ac83-7948e92353d5,
  abstract     = {A general expression for the distribution of the fluctuating 2(l)-pole moment M(l) of a spherical sample of dielectric material is derived on the basis of dielectric theory combined with statistical mechanics. The formulas are compared with results from computer simulations of a weakly coupled Stockmayer fluid and the agreement is shown to be excellent. Furthermore, we calculate the size of the coupling, quantified through the free energy of solvation A(solv), of the fluctuating electric moments to a surrounding dielectric medium. It turns out that the contribution to A(solv) from each fluctuating electric moment actually increases with increasing order l of the moment, resulting in a formally infinite free energy of solvation. We also present a correction to A(solv) for molecular media, which shows that the molecular nature of the surrounding medium effectively suppresses the divergence in the solvation free energy.},
  articleno    = {124521},
  author       = {Stenhammar, Joakim and Linse, Per and Malmqvist, Per-Åke and Karlström, Gunnar},
  issn         = {0021-9606},
  language     = {eng},
  number       = {12},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Electric multipole moment fluctuations in polar liquids.},
  url          = {http://dx.doi.org/10.1063/1.3100312},
  volume       = {130},
  year         = {2009},
}