Nonlocal statistical field theory of dipolar particles in electrolyte solutions

Journal of Physics. Condensed Matter : an Institute of Physics Journal
Yury A Budkov

Abstract

We present a nonlocal statistical field theory of a dilute electrolyte solution with a small additive of dipolar particles. We postulate that every dipolar particle is associated with an arbitrary probability distribution function (PDF) of distance between its charge centers. Using the standard Hubbard-Stratonovich transformation, we represent the configuration integral of the system in the functional integral form. We show that in the limit of a small permanent dipole moment, the functional in integrand exponent takes the well known form of the Poisson-Boltzmann-Langevin (PBL) functional. In the mean-field approximation we obtain a non-linear integro-differential equation with respect to the mean-field electrostatic potential, generalizing the PBL equation for the point-like dipoles obtained first by Abrashkin et al. We apply the obtained equation in its linearized form to derivation of the expressions for the mean-field electrostatic potential of the point-like test ion and its solvation free energy in salt-free solution, as well as in solution with salt ions. For the 'Yukawa'-type PDF we obtain analytic relations for both the electrostatic potential and the solvation free energy of the point-like test ion. We obtain a genera...Continue Reading

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Citations

Dec 18, 2018·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Sahin BuyukdagliRalf Blossey
Apr 10, 2020·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Yury A Budkov, Andrei Kolesnikov
Jun 25, 2020·Physical Chemistry Chemical Physics : PCCP·Yury A Budkov
Feb 20, 2020·Physical Review. E·Yael AvniDavid Andelman
May 20, 2020·Physical Review. E·Nikolai V BrilliantovYury A Budkov
Apr 1, 2021·Journal of Chemical Theory and Computation·Jun HuangMichael Eikerling
Sep 16, 2021·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Lulu ZhangJun Huang

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