The Clausius-Mossotti and Mott-Littleton theories of the static dielectric constant of alkali halide crystals

Shanker, J.; Agrawal, G. G.; Singh, R. P.

doi:10.1080/13642817908245811

Cited by 6 publications

(4 citation statements)

References 13 publications

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“…However, it should be pointed out that the greatest discrepancies arise for those systems, namely LiCl and LiBr, for which the results derived from (3.2) relied on values of [Vd ∞ /dV] V)Ve which do not originate from experiment. For these two systems, the [Vd ∞ /dV] V)Ve values in Table 5 were estimated 59 using the method of fractional change. 60 Evidence that this method significantly overestimates [dR A /dR] R)Re is provided by the case of NaI for which this method yields 59 a value of -1.280 for [Vd ∞ /dV] V)Ve which is significantly different from that of -1.6959 (Table 5) derived directly from experiment.…”

Section: Distance and Structural Dependencies Of The Anion Polarizabi...mentioning

confidence: 99%

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Polarizability of the Iodide Ion in Crystal

Bichoutskaia

Pyper

2007

J. Phys. Chem. C

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The electronic dipole polarizability of the iodide ion in solid cubic NaI and KI is derived from ab initio electronic structure computations as function of closest cation-anion separation for the four-coordinated zinc blende structure, the 6-fold coordinated rock salt structure, and the 8-fold coordinated phase having the CsCl structure. The contributions from electron correlation were computed using Moller-Plessett perturbation theory taken to the second order. For both NaI and KI, the anion polarizability predicted for the observed rock-salt polymorph at the equilibrium separation agrees well with the value deduced from experiment. The anion polarizabilities increase with both decreasing coordination number at constant distance and with increasing distance at constant coordination number. Both the polarizabilities and their contributions from electron correlation are suppressed in-crystal relative to those computed for the free iodide ion. The ab initio predictions for the derivatives of the anion polarizabilities with respect to closest cation-anion separation are slightly smaller than those deduced from the experimental observations. Reviews of both the latter and the dipole polarizability derivatives previously computed for other alkali halides are presented. The distance dependence of the polarizability of the iodide ion in the point charge representation of the rock-salt lattice, computed ab initio, differs in shape slightly but significantly from that for either NaI or KI. This difference prevents the in-crystal polarizabilities and their distance derivatives from being predicted by shifting the point lattice polarizability function as previously shown to be possible for the salts of the lighter halides. The applicability of the light scattering model description of anion polarizabilities in condensed phases is investigated.

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Section: Distance and Structural Dependencies Of The Anion Polarizabi...mentioning

confidence: 99%

“…I - present work. b [ V dε ∞ /d V ] V = V e from refs and calculated using the method of fractional change. Values bracketed are not truly experimental.…”

Section: Ab Initio Polarizability Predictionsmentioning

confidence: 99%

Polarizability of the Iodide Ion in Crystal

Bichoutskaia

Pyper

2007

J. Phys. Chem. C

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“…The experimental derivatives are also often expressed in terms of another dimensionless property, − V m dε ∞ /d V m (see, for example, ref and references therein), which is related to ρ(d n /dρ) by …”

Section: Comparison With Experimentsmentioning

confidence: 99%

Environmental Effects on Anion Polarizability: Variation with Lattice Parameter and Coordination Number

Jemmer¹,

Fowler²,

Wilson³

et al. 1998

J. Phys. Chem. A

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The results of ab initio calculations of in-crystal ionic polarizabilities, α, over a wide range of lattice parameters, R, are presented for LiF, NaF, KF, LiCl, NaCl, KCl, LiBr, NaBr, KCl, and MgO. The derivatives of the mean polarizability with respect to lattice parameters are compared with experimental values obtained from the variation of the refractive index with pressure. The environmental effects on the polarizability of an anion may be viewed as the consequence of imposition of a confining potential on its electron density whose origin includes Coulombic interactions and the exclusion of these electrons from the region occupied by the electron density of the first-neighbor shell of cations. This model suggests scaling relationships, between values of α(R) obtained at different levels of calculation and for a given anion with different cations, which are shown to be semiquantitative. These findings lead to the proposal of a universal representation of the polarizability of a given anion, which predicts the dependence on lattice parameter and crystal form and transfers from one substance to another.

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“…Electric permittivity from Eq. (2) with εr,∞ = 2.31, ε r,0 = 5.90 23 for the sodium chloride crystal. part remains positive.…”

Section: Surface Modes In a Thin Filmmentioning

confidence: 99%

Infrared active surface modes found in thin films of perfluoroalkanes reveal the dipole–dipole interaction and surface morphology

Fukumi

Shimoaka

Shioya

et al. 2020

The Journal of Chemical Physics

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Infrared (IR) spectra of an organic thin film are mostly understood by considering the normal modes of a single molecule, if the dipole-dipole (D-D) interaction is ignorable in the film. When the molecules have a chemical group having a large permanent dipole moment such as the C= =O and C− −F groups, the D-D interaction induces vibrational couplings across the molecules, which produces an extra band as a surface phonon or polariton band because of the small thickness. Since the dipole moment of an organic compound is much less than that of an inorganic ionic crystal, we have a problem that the extra band looks like a normal-mode band, which are difficult to be discriminated from each other. In fact, this visual similarity sometimes leads us to a wrong direction in chemical discussion because the direction of the transition moment of the extra band is totally different from those of the normal modes. Here, we show useful selection rules for discussing IR spectra of a thin film without performing the permittivity analysis. The apparent change in the spectral shape on decrease in the thickness of the sample can be correlated with the morphological change in the film surface, which can also be discussed with changes in the molecular packing. This analytical technique has effectively been applied for studying the chemical properties of perfluoroalkanes as a chemical demonstration, which readily supports the stratified dipole-array theory for perfluoroalkyl compounds.

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The Clausius-Mossotti and Mott-Littleton theories of the static dielectric constant of alkali halide crystals

Cited by 6 publications

References 13 publications

Polarizability of the Iodide Ion in Crystal

Polarizability of the Iodide Ion in Crystal

Environmental Effects on Anion Polarizability: Variation with Lattice Parameter and Coordination Number

Infrared active surface modes found in thin films of perfluoroalkanes reveal the dipole–dipole interaction and surface morphology

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