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:
http://lup.lub.lu.se/record/1392571
 author
 Stenhammar, Joakim ^{LU} ; Linse, Per ^{LU} ; Malmqvist, PerÅke ^{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
 publisher
 American Institute of Physics
 external identifiers

 wos:000264775200067
 pmid:19334865
 scopus:63649098966
 ISSN
 00219606
 DOI
 10.1063/1.3100312
 language
 English
 LU publication?
 yes
 id
 cf3cd297ec9c413dac837948e92353d5 (old id 1392571)
 alternative location
 http://jcp.aip.org/resource/1/jcpsa6/v130/i12/p124521_s1
 date added to LUP
 20090506 13:15:19
 date last changed
 20180107 05:09:38
@article{cf3cd297ec9c413dac837948e92353d5, 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, PerÅke and Karlström, Gunnar}, issn = {00219606}, 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}, }