Electric multipole moment fluctuations in polar liquids.
(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:
https://lup.lub.lu.se/record/1392571
- author
- Stenhammar, Joakim LU ; Linse, Per LU ; Malmqvist, Per-Åke LU and Karlström, Gunnar LU
- organization
- publishing date
- 2009
- 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
- 2023-01-02 20:59:44
@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}},
}