Zintl Salts Ba2P7X (X = Cl, Br, and I): Synthesis, Crystal, and Electronic Structures

Dolyniuk, Juli‐Anna; Kovnir, Kirill

doi:10.3390/cryst3030431

Cited by 15 publications

(26 citation statements)

References 28 publications

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“…Despite some deviations of the angles in the layered P 3 2− found in mP ‐BaP 3 from regular tetrahedral angles, no displacement of the ELF maxima from the line connecting atoms was observed. This is in contrast to the more strained isolated polyphosphide cage, P 7 3− , found in Ba 2 P 7 I in which ELF maxima are shifted from the edges of the base triangle 23. The observed ELF distribution allows for the qualification of both mS ‐BaP 3 and mP ‐BaP 3 as classical Zintl phases.…”

Section: Resultsmentioning

confidence: 69%

“…We confirm that mS ‐BaP 3 can indeed be produced either from the reactions of elements at temperatures above 1150 K or by the use of small amounts of iodine as a transport agent. In the latter case, mS ‐BaP 3 formed at temperatures as low as 1073 K. However, iodine proved to be very reactive, and the reactions with more than a few crystals of I 2 led to the formation of Ba 2 P 7 I 23. To clarify the mS / mP phase relationship, we performed differential scanning calorimetry (DSC) characterizations of BaP 3 samples (Figure 1).…”

Section: Resultsmentioning

confidence: 99%

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mP‐BaP₃: A New Phase from an Old Binary System

Dolyniuk

Kaseman

Sen

et al. 2014

Chemistry A European J

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A polyphosphide, mP-BaP3, with a unique two-dimensional phosphorus layer has been discovered and characterized. It crystallizes in the monoclinic space group P2₁/c with unit-cell parameters a=6.486(1), b=7.710(1), c=8.172(2) Å; β=104.72(3)°; Z=4. Its phosphorus polyanion can be derived from the strong elongation of 2/3 of the P-P bonds present in the layers of black phosphorus. The unit-cell volume of the mP-BaP3 phase is 1.4% larger than the volume of another polymorph, mS-BaP3, reported more than 40 years ago. The latter phase features the presence of one-dimensional phosphorus chains separated by Ba atoms. The differences in the structures of the phosphorus fragments in both polymorphs of barium triphosphide result in large differences in both the thermal stability of these materials as well as in their properties as evidenced by DSC, (31)P solid-state MAS NMR, UV/Vis, and surface photovoltage spectroscopies, alongside quantum-chemical calculations.

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Section: Resultsmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

mP‐BaP₃: A New Phase from an Old Binary System

Dolyniuk

Kaseman

Sen

et al. 2014

Chemistry A European J

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“…Polyphosphides are known to form a variety of crystalline structures with different elements [1][2][3]. The electronic structures of polyphosphides can be rationalized by the application of the Zintl concept [4,5].…”

Section: Introductionmentioning

confidence: 99%

“…In A 3 P 7 , (A = alkali metal) an electron is given from each atom A to allow the formation of the cage P −3 7 [1,6], in Ba 3 P 14 , three Ba atoms each give two electrons to allow the formation of two cages P −3 7 [7], in Ba 2 P 7 Cl Zintl salt, the total charge of two Ba +2 cations is compensated by a combination Cl − of and P −3 anions. Juli-Anna Dolyniuk and Kirill Kovnir [1] have shown that the Ba 2 P 7 Br and Ba 2 P 7 I isostructurally include the family of P −3 7 structures. A large number of Zint compounds have recently been synthesized and these structures offer abundant and interesting physical properties, such as semi-conductivity, superconductivity.…”

Section: Introductionmentioning

confidence: 99%

“…A large number of Zint compounds have recently been synthesized and these structures offer abundant and interesting physical properties, such as semi-conductivity, superconductivity. In a recent experimental study, Juli-Anna Dolyniuk and Kirill Kovnir [1] synthesized the new Zintl phase Ba 2 P 7 X We have used the experiment lattice constant to start calculating the parameters of the lattice (a, b and c), the angle β and the internal atomic coordinates. The calculated equilibrium crystal parameters for Ba 2 P 7 X are presented in table 1 and table 2 along with the available experimental data [16] for the sake of comparison.…”

Section: Introductionmentioning

confidence: 99%

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Investigation of structural and elastic properties of monoclinic Ba2P7X (X = Cl, Br, I) Zintl Salts compounds

Radjai¹,

Maouche²,

Guechi³

et al. 2019

Condens. Matter Phys.

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Structural and elastic properties of Ba 2 P 7 X (X=Cl, Br, I) ( Barium Phosphide Halides) Zintl compounds have been investigated using the pseudo-potential plane-wave (PP-PW) method based on the density functional theory (DFT) within the generalized gradient approximation (GGA-PBESOL). The calculated lattice constants and internal parameters are in a good agreement with the experimental results reported in literature. In this paper, we present an investigation of the relative changes of the structural parameters and elastic constants as function of hydrostatic pressure. Isotropic elastic moduli and their related properties for single-crystal and polycrystalline phase, including the namely bulk modulus, shear modulus, Young's modulus, Poisson's ratio, elastic anisotropy indexes, Pugh's indicator of brittle/ductile behavior, elastic wave velocities and Debye temperature have been estimated from C i j using Voigt, Russ and Hill approximations. Two different methods have been used to study the elastic anisotropy of these compounds.M. Radjai et al.(barium and indium phosphide) and analyzed its crystalline structure. According to [1], both compounds Ba 2 P 7 Br and Ba 2 P 7 I are crystallized in a new type of monoclinic structure in space group P2 1 /m (No. 11) and are isostructural to Ba 2 P 7 Cl [1]. The crystal structures of Ba 2 P 7 X (X = Cl, Br, I) exhibit the presence of P −3 7 groups with halogenated anions and barium cations. Authors think that neither theoretical nor experimental studies of the elastic properties had been carried out. Therefore, such calculations are made in the present work with the inclusion of pressure effects. The results reported in this paper may be useful for evaluating the potential technological applications of Ba 2 P 7 X. Knowledge of the elastic constants of crystalline materials is essential to understand many of their basic physical properties. In particular, these constants provide information on the stability and stiffness of the material against externally applied stresses [8]. Knowledge of the pressure dependence of elastic constants and lattice parameters is significant for many modern technologies [8,9]. Computational detailsCurrently, there are different theoretical calculation codes with different approximations. In our calculations, we use the code CASTEP (CambridgeSerial Total Energy Package) [10] which is a direct application of the calculation. All calculations were performed using pseudo-potential plane wave ab initio (PP-PW) method based on the density function (DFT). To determine the structural parameters and elastic moduli of the considered compounds, there was used a new version of the generalized gradient approximation (GGA), namely the GGA-PBEsol [11], which has been developed specifically to improve the description of the exchange-correlation in solids. In all electronic total energy calculations, an ultrasoft Vanderbilt pseudo-potential [12] was used to treat the potential seen by the valence electrons due to the nucleus and electrons of the frozen nucleus. B...

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A Theoretical Investigation of the Stability, Electronic, Optical, and Thermoelectric Properties of BaLiP

Dusabe

Dongho-Nguimdo

Joubert

2021

Physica Status Solidi (b)

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The density functional theory and post density functional theory techniques are used to investigate the properties of BaLiP for potential applications in photovoltaic and thermoelectric (TE) applications. Density functional calculations of the cohesive energy, phonon‐dispersion, and elastic constant studies establish structural, dynamical, and mechanical stability of the compound. Density functional calculations show that BaLiP is a direct bandgap semiconductor while optical properties at the Bethe–Salpeter equation level of approximation suggest that BaLiP is anisotropic with the optical bandgaps of 2.22 and 1.59 eV for in‐plane and out‐of‐plane absorption, respectively. A maximum absorption coefficient of 4.35×105 cm−1 for in‐plane and 5.02×105 cm−1 for out‐of‐plane absorption in the visible range at 2.69 and 2.63 eV is found, respectively. Lattice thermal conductivity is computed using a Boltzmann transport equation approach. The calculations reveal that the average lattice thermal conductivity is 2.495 Wm−1normalK−1 at room temperature. The figure of merit, which is the main criterion for estimating the TE potential of a material, is estimated to have a maximum of 0.6 at 1000 K at a hole carrier concentration of 1019 cm−3. This study shows that BaLiP has some promise as a candidate for applications in electronics, optoelectronics, and TE applications.

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Zintl Salts Ba2P7X (X = Cl, Br, and I): Synthesis, Crystal, and Electronic Structures

Cited by 15 publications

References 28 publications

mP‐BaP₃: A New Phase from an Old Binary System

mP‐BaP₃: A New Phase from an Old Binary System

Investigation of structural and elastic properties of monoclinic Ba2P7X (X = Cl, Br, I) Zintl Salts compounds

A Theoretical Investigation of the Stability, Electronic, Optical, and Thermoelectric Properties of BaLiP

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Zintl Salts Ba2P7X (X = Cl, Br, and I): Synthesis, Crystal, and Electronic Structures

Cited by 15 publications

References 28 publications

mP‐BaP3: A New Phase from an Old Binary System

mP‐BaP3: A New Phase from an Old Binary System

Investigation of structural and elastic properties of monoclinic Ba2P7X (X = Cl, Br, I) Zintl Salts compounds

A Theoretical Investigation of the Stability, Electronic, Optical, and Thermoelectric Properties of BaLiP

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mP‐BaP₃: A New Phase from an Old Binary System

mP‐BaP₃: A New Phase from an Old Binary System