A general expression for the distribution of the fluctuating -pole moment 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 , of the fluctuating electric moments to a surrounding dielectric medium. It turns out that the contribution to from each fluctuating electric moment actually increases with increasing order of the moment, resulting in a formally infinite free energy of solvation. We also present a correction to for molecular media, which shows that the molecular nature of the surrounding medium effectively suppresses the divergence in the solvation free energy.
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Research Article| March 31 2009
Electric multipole moment fluctuations in polar liquids
Joakim Stenhammar, Per Linse, Per-Åke Malmqvist, Gunnar Karlström; Electric multipole moment fluctuations in polar liquids. J. Chem. Phys. 28 March 2009; 130 (12): 124521. https://doi.org/10.1063/1.3100312
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