The Lattice Energies of the Alkaline Earth Halides

Brackett, Thomas E.; Brackett, Elizabeth

doi:10.1021/j100894a062

Cited by 19 publications

(7 citation statements)

References 1 publication

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“…The L-values calculated without due account for E , coincide, in essence, with our previous results [12] and those of Brackett and Brackett [13], who also took account of Van der Waals interactions. However, both these results differ strongly from the experimental Lexp (last column, Table 3).…”

Section: ( 7 )supporting

confidence: 89%

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Energy of Anion Polarization in Layered Structures

Urusov

Dudnikova

1982

Physica Status Solidi (b)

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I n layered structures the anion position has low local symmetry. The result are induced anion dipoles which strongly interact with each other and with all the remaining crystalline matrix. Two different sppronchcs are examined t o take account of the anion polarization energy in layered structures. The lattice energy is calculated with regard to the anion polarization term for some halides of bivalent metals (Mg, Ca, Cd, Mn, Pb). The polarization correction t o lattice energy is found to be large, 3 to 4 eV. Impurity dissolution energies are recalculated for those cases where the pure impurity component forms a layered structure: their values are found t o be positive and correct in order of magnitude.

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Section: ( 7 )supporting

confidence: 89%

“…Van der Waals interaction C/Rs (values of C are taken from [13]). This correction to the lattice energy is only 0.1 to 0.5 eV.…”

Section: ( 7 )mentioning

confidence: 99%

Energy of Anion Polarization in Layered Structures

Urusov

Dudnikova

1982

Physica Status Solidi (b)

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“…The present paper collects together the results of published Madelung constant calculations (with charges included) for a large number of ionic solids − and demonstrates their relation to corresponding Madelung energies. Unfortunately, many of the sources of published Madelung constants for more complex materials fail to give explicitly the reference distance, l o , to which the Madelung constant refers.…”

Section: Introductionmentioning

confidence: 88%

Solid-State Energetics and Electrostatics: Madelung Constants and Madelung Energies

Glasser

2012

Inorg. Chem.

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The Madelung constants of ionic solids relate to their geometry and electrostatic interactions. Furthermore, because of issues in their evaluation, they are also of considerable mathematical interest. The corresponding Madelung (electrostatic, coulomb) energy is the principal contributor to the lattice energies of ionic systems, and these energies largely influence many of their physical properties. The Madelung constants are here defined and their properties considered. A difficulty with their application is that they may be defined relative to various lattice distances, and with various conventions for inclusion of the charges, leading to possible confusion in their use. Instead, the unambiguous Madelung energy, E(M), is to be preferred in chemistry. An extensive list of Madelung energies is presented. From this data set, it is observed that there is a strong linear correlation between the lattice energies of ionic solids, U(POT), and their Madelung energies: U(POT)/kJ mol(-1) = 0.8519E(M) + 293.9. This correlation establishes that the lattice energy, U(POT), for ionic solids is about 15% smaller than the attractive Madelung energy, the difference arising from the repulsions unaccounted for by the solely coulombic Madelung energy calculation. Correlations of U(POT) against E(M) for alkali metal hydrides and transition metal compounds, each having considerable covalency, show much reduced Madelung contributions to the lattice energy. These correlations permit ready estimation of lattice energies, and are the first to be based on actual data rather than a broad analysis. The independent volume-based thermodynamic (VBT) method, which relies on a separate correlation with the formula unit volume of the ionic material, complements these correlations.

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“…The last term takes into account the dipole-dipole van der Waals interaction. A similar equation was used in [7], where the repulsion parameters averaged over fluorides were taken as the parameters for all the halides of alkaline earths. A satisfactory agreement between the calculated and experimental L, values was obtained for most of the substances ; however, the discrepancy between the theoretical and experimental results reached 1.5 to 4 eV for a number of compounds (see Table 1).…”

Section: Calculation Methodsmentioning

confidence: 99%

“…Table 1 lists the initial parameters and calculation results which are compared with the values reported in [7] and the experimental ones. As is evident from these data, the ionic model is sufficient to calculate L, of most alkaline-earth metal halides and gives underestimated values for magnesium halides (except for MgF,) and CaI, in conformity with [7]. This leads to unreal negative Q values.…”

Section: All the Three Calculation Methods Give Close Values Of Lmentioning

confidence: 99%

Calculations of Solution Energies of Alkaline‐Earth Metal Ions in Alkali Halide Crystals

Urusov¹,

Dudnikova²,

Garanin³

1980

Physica Status Solidi (b)

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The Born-Mayer ionic theory of lattice energy is used to solve the problem of solution of B2+ ions in AX crystals with NaCl structure (A alkali metal, B alkaline-earth metal, X halogen). About fifty combinations of initial parameters are obtained, by varying the ionic radii, polarizabilities, repulsion parameters, and pure AX and BX, lattice energies. For example, there are four variants of the repulsion parameters: average ones and those determined from the elastic, dielectric, and atomic spectral properties. The model is sufficiently accurate to yield reasonable values of solution energies for the most ionic impurity lattices (all fluorides, barium and strontium chlorides). Both, the "polarization catastrophe" (for large impurity ions on small cation sites) and lack of an ionic model for the Mg2+ impurities (except for fluoride) and all iodides are considered to be the main factors which reduce the calculation validity.Die ionische Born-Mayer-Theorie der Gitterenergie wird benutzt, um das Problem der Losung von B2+-Ionen in AX-Kristallen mit NaC1-Struktnr (A-Alkalimetall; B-Erdalkalimetall; X-Halogen) aufzuklaren. Etwa funfzig Kombinationen von Anfangsparametern werden durch Variation der Ionenradien, Polarisierbarkeiten, AbstoBungsparameter sowie reinen AX-und BX,-Gitterenergien erhalten. Zum Beispiel existieren vier Varianten von AbstoBungsparametern : gemittelte und aus den elastischen, dielektrischen und atomspektralen Eigenschaften bestimmte. Das Modell ist genugend genau, um vernunftige Werte der Losungsenergien fur die meisten ionischen Storstellengitter (alle Fluoride, Barium-und Strontioumchlorid) zu erhalten. Sowohl die ,,Polarisationskatastrophe" (fur groBe Storstellenionen und kleine Kationenplatze) als auch das Fehlen eines Ionenmodells fur die Mg2+-Storstellen (auBer fur Fluoride) und alle Jodide werden als Hauptfaktoren betrachtet, die die Gultigkeit der Berechnung reduzieren.

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The Lattice Energies of the Alkaline Earth Halides

Cited by 19 publications

References 1 publication

Energy of Anion Polarization in Layered Structures

Energy of Anion Polarization in Layered Structures

Solid-State Energetics and Electrostatics: Madelung Constants and Madelung Energies

Calculations of Solution Energies of Alkaline‐Earth Metal Ions in Alkali Halide Crystals

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