Cavity Concept in Dielectric Theory

Linder, Bruno; Hoernschemeyer, Donald

doi:10.1063/1.1840740

Cited by 29 publications

(36 citation statements)

References 16 publications

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“…Other parametrizations, commonly resulting in effective radii between R 0 and R 1 , are of course also possible. In particular, perturbation models of dipole solvation 32,33 suggest the following expression for the effective cavity radius:…”

Section: Reaction Fieldmentioning

confidence: 99%

Microscopic fields in liquid dielectrics

Martin

Matyushov

2008

The Journal of Chemical Physics

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We present the results of an analytical theory and numerical simulations of microscopic fields in dipolar liquids. Fields within empty spherical cavities (cavity field) and within cavities with a probe dipole (directing field) and the field induced by a probe dipole in the surrounding liquid (reaction field) are considered. Instead of demanding the field produced by a liquid dielectric in a large-scale cavity to coincide with the field of Maxwell's dielectric, we continuously increase the cavity size to reach the limit of a mesoscopic dimension and establish the continuum limit from the bottom up. Both simulations and analytical theory suggest that the commonly applied Onsager formula for the reaction field is approached from below, with increasing cavity size, by the microscopic solution. On the contrary, the cavity and directing fields do not converge to the limit of Maxwell's dielectric. The origin of the disagreement between the standard electrostatics and the results obtained from microscopic models is traced back to the failure of the former to account properly for the transverse correlations between dipoles in molecular liquids. A new continuum equation is derived for the cavity field and supported by numerical simulations. Experimental tests of the theoretical results are suggested.

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Section: Reaction Fieldmentioning

confidence: 99%

Microscopic fields in liquid dielectrics

Martin

Matyushov

2008

The Journal of Chemical Physics

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“…Схожие численные результаты получаются, если применить формулы работы [2] с реалистическими значениями онзагеровского радиуса, рассчитанного по методу Линдера и Херншемайера [22]. Используя графики работ [2,17], можно заключить, что поправка интенсивности на эффект RF в таком случае становится весьма малой.…”

Section: ап коузов ни егорова ан добротворскаяunclassified

Квантовая Модель Диполь-Индуцированный Диполь И Влияние Инертного Окружения На Интенсивность ИК Поглощения

Коузов¹,

Егорова²,

Добротворская³

2019

Журнал Технической Физики

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Based on the diagrammatic techniques, a theory of the imaginary part of the isotropic polarizability induced by the dipole-dipole interactions between isotropically polarizable particles is elaborated. A classification of single infrared resonances corresponding to cases of the allowed and interaction-induced absorption bands is proposed. The Dipole-Induced-Dipole (DID) diagrammatic terms causing the allowed intensity variations via the reaction-field effect are analytically summed up. The thus-derived rigorous results are in conflict with the semi-empirical Onsager-Bottcher model. For the simplest reference systems (cryogenic solutions of HCl and HBr), our numerical estimations demonstrate the reaction-field contributions to observed intensity variations of vibrational bands to be weak and to become even weaker with a growth of the solvent particle dimensions that suggests the inadequacy of the DID and Onsager-Bottcher models to experimental data.

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“…This particular solution exemplifies the general result that the cavity radius cannot be defined as a constant even for a given solvent/solute combination and needs instead to be a function of the solvent thermodynamic state. 16,17 Assuming a = Const gives unreliable values for the solvation entropy and, most likely, for other thermodynamic derivatives of the solvation free energy. 16,[18][19][20] What we show here is that the dependence of the cavity size on both the thermodynamic state of the solvent and on the solute-solvent potential can be accommodated in terms of the solute-solvent radial distribution function.…”

Section: Introductionmentioning

confidence: 99%

Free energy of ion hydration: Interface susceptibility and scaling with the ion size

Dinpajooh

Matyushov

2015

The Journal of Chemical Physics

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Free energy of solvation of a spherical ion in a force-field water is studied by numerical simulations. The focus is on the linear solvation susceptibility connecting the linear response solvation free energy to the squared ion charge. Spherical hard-sphere solutes, hard-sphere ions, and Kihara solutes (Lennard-Jones modified hard-sphere core) are studied here. The scaling of the solvation susceptibility with the solute size significantly deviates from the Born equation. Using empirical offset corrections of the solute size (or the position of the first peak of the solute-solvent distribution function) do not improve the agreement with simulations. We advance a new perspective on the problem by deriving an exact relation for the radial susceptibility function of the interface. This function yields an effective cavity radius in the Born equation calculated from the solute-solvent radial distribution function. We find that the perspective of the local response, assuming significant alteration of the solvent structure by the solute, is preferable compared to the homogeneous approximation assuming intact solvent structure around the solute. The model finds a simple explanation of the asymmetry of hydration between anions and cations in denser water shells around anions and smaller cavity radii arising from the solute-solvent density profiles.

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Cavity Concept in Dielectric Theory

Cited by 29 publications

References 16 publications

Microscopic fields in liquid dielectrics

Microscopic fields in liquid dielectrics

Квантовая Модель Диполь-Индуцированный Диполь И Влияние Инертного Окружения На Интенсивность ИК Поглощения

Free energy of ion hydration: Interface susceptibility and scaling with the ion size

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