Summary_eng (Статистическое описание многочастичных эффектов в классических ион-молекулярных системах), страница 11

As30is known, for the exible synthetic polymers this assumption appears quite reasonable [Gurovich,Macromolecules,1994; Gurovich, Macromolecules, 1995]. Second restriction of the proposed modelsis related to the fact that for the description of the conformational behavior of the polymer chainin the electric eld only one order parameter is used, that is the gyration radius of the chain, whichallows one to control the change of the polymer volume, but does not allow one to understandanything about the change of its form.

Nevertheless, from the general considerations it is clear,that this restriction is not that serious at the electric eld strengths, at which only a slight swellingof the polymer happens, i.e. which do not lead to the suciently strong extension of the polymerchain along the eld direction due to the mechanical orientation of the monomers. Moreover, theseelds must not lead to the electrolysis of the solvent molecules.

Apparently, such elds must havestrength much smaller than the strengths of the intermolecular elds (∼ 108 − 109 V /m). Besidesthat, it is mentioned, that within the examined models the dipole correlations of the monomers,related to the uctuations of the dipole moments of the monomers, have not been taken into account.It can be shown [Budkov and Kolesnikov, Eur. Phys. J. E., 2016], that the consideration of thedipole correlations will not qualitatively change eventual results, but only shift parameters regions(polarizability and eld strength), where the discussed eects are presented.ConclusionIn chapterConclusion the following outcomes were summarized:ˆ It was developed a formalism, based on the classical density functional theory, allowing oneto obtain self-consistent eld equations, taking into account presence of the solvent moleculesin the electrolyte solution, possessing constant dipole moment and/or polarizability.ˆ Basing on the developed formalism, theory of the electrical double layer at the metal electrode/liquid electrolyte interface was formulated with account for the polar or polarizableimpurity molecules, present in the bulk phase.

On the basis of the developed theory the behavior of the dierential capacitance of the electrical double layer as a function of the dipolemoment, polarizability of the co-solvent molecules and its concentration, and also specicinteractions between the components of the mixture was investigated.ˆ A non-local eld-theoretic model of the electrolyte solution with a small additive of the dipolar particles with polar groups, located at the long enough uctuating distances between eachother, was developed. In terms of formulated model the self-consistent eld equation, generalizing the well-known Poisson-Boltzmann-Langevin equation, for the electrostatic potential,created by the external charges in the electrolyte solution in the presence of the particles withsuciently long dipole moments, was obtained.

A general relation for the electrostatic freeenergy of the electrolyte solution with the additive of the long enough dipolar particles withinthe Gaussian approximation was obtained.ˆ It was formulated a Flory-de Gennes type model of the weak polyelectrolyte macromoleculewith account for the many-body dipole correlations of the monomers. A coil-globule transitionof the weak polyelectrolyte macromolecule, induced by the dipole-dipole interactions of themonomers with the many-body eects consideration, was investigated within developed model.A good agreement between the theoretical and MD simulations results was achieved.ˆ A Flory-de Gennes type model of the exible dielectric polymer chain, dissolved in the liquiddielectric under the constant uniform electric eld with isotropically polarizable monomers wasformulated. A conformational behavior of the exible dielectric polymer chain in the constantuniform electric eld in the regimes of good and poor solvents was investigated.

A newconformational coil-globule transition, induced by the electrostrictive swelling of the polymerin the electric eld was predicted. An essential possibility of the control of the conformationalstate of the polymer by the change of the electric eld strength has been presented.31ˆ Model of the dielectric polymer chain with isotropically polarizable monomers in the mediumof the dielectric solvent with a small additive of the isotropically polarizable particles ofthe low-molecular target compound in the external electric eld was developed.

Within thedeveloped model the behavior of the local concentration of the low-molecular particles ofthe target compound within the polymer volume as a function of the relation between thepolarizabilities of the monomer units and particles of the target compound was investigated.AppendixIn the Appendix the appliance of the path integration to the calculation of the distributionfunction over the gyration radius of the Gaussian polymer chain in d-dimensional space has beenshown.

Basing on the obtained asymptotic relations for the distribution function at large and smallgyration radii, the interpolation formula for the conguration entropy as a function of the gyrationradius of the Gaussian polymer chain in d-dimensional space has been constructed, used in theChapters 4-5 for the description of the conformational entropy contribution of the polymer chain inthe case of d = 3.32Bibiliography1. Budkov Yu.A., Kolesnikov A.L. and Kiselev M.G. A modied Poisson-Boltzmann theory: Eectsof co-solvent polarizability // EPL.

2015. V.111. P. 28002. https://doi.org/10.1209/02955075/111/280022. Budkov Yu.A., Kolesnikov A.L., Kiselev M.G. On the theory of electric double layer withexplicit account of a polarizable cosolvent // J. Chem. Phys. 2016. V.144. P. 184703.https://doi.org/10.1063/1.49486343. Budkov Y., Kolesnikov A., Goodwin Z., Kiselev M., Kornyshev A.

Theory of electrosorption of water from ionic liquids // Electrochimica Acta. 2018. V. 284. P. 346-354.http://doi.org/10.1016/j.electacta.2018.07.1394. Budkov Y. Nonlocal statistical eld theory of dipolar particles in electrolyte solutions// Journal of Physics: Condensed Matter. 2018. V. 30. P. 344001-344009.http://doi.org/10.1088/1361-648X/aad3ee5. Budkov Yu.A. and Kolesnikov A.L.

Polarizable polymer chain under external electric eld:Eects of many-body electrostatic dipole correlations // Eur. Phys. J. E. 2016. V.39. P.110. http://doi.org/10.1140/epje/i2016-16110-x6. Budkov Yu.A., Kalikin N.N. and Kolesnikov A.L. Polymer chain collapse inducedby many-body dipole correlations // Eur. Phys. J. E. 2017. V.40. P. 47.http://doi.org/10.1140/epje/i2017-11533-57. Gordievskaya Yu.D., Budkov Yu.A. and Kramarenko E.Y. An interplay of electrostatic and excluded volume interactions in the conformational behavior of a dipolarchain: theory and computer simulations // Soft Matter 2018.

V.14. P. 3232.http://doi.org/10.1039/C8SM00346G8. Budkov Yu.A., Kolesnikov A.L. and Kiselev M.G. Communication: Polarizable polymer chainunder external electric eld in a dilute polymer solution // The Journal of chemical physics 2015. V.143. P. 201102. http://doi.org/10.1063/1.49366619. Kolesnikov A.L., Budkov Yu.A., Basharova E. and Kiselev M.G. Statistical theory of polarizabletarget compound impregnation into a polymer coil under the inuence of an electric eld //Soft Matter 2017. V.13. P. 4363. http://doi.org/10.1039/C7SM00417F10.

Budkov Yu.A. and Kiselev M.G. Flory-type theories of polymer chains under dierent externalstimuli // J. Phys.: Condens. Matter. 2018. V.30. P. 043001. http://doi.org/10.1088/1361648X/aa9f5611. Budkov Yu.A. and Kolesnikov A.L. On a new application of the path integrals in polymerstatistical physics // J. Stat. Mech. 2016. V.2016. P. 103211. http://doi.org/10.1088/17425468/2016/10/10321133.