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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)
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; ; and
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type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
130
issue
12
article number
124521
publisher
American Institute of Physics (AIP)
external identifiers
  • wos:000264775200067
  • pmid:19334865
  • scopus:63649098966
  • pmid:19334865
ISSN
0021-9606
DOI
10.1063/1.3100312
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: Physical Chemistry 1 (S) (011001006), Theoretical Chemistry (S) (011001039)
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
2016-04-01 11:37:30
date last changed
2021-09-22 05:22:39
@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.},
  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 (AIP)},
  series       = {Journal of Chemical Physics},
  title        = {Electric multipole moment fluctuations in polar liquids.},
  url          = {https://lup.lub.lu.se/search/files/2566080/1977771.pdf},
  doi          = {10.1063/1.3100312},
  volume       = {130},
  year         = {2009},
}