Lattice Energies and Thermochemistry of Hexahalometallate(iv) Complexes, A2MX6, Which Possess the Antifluorite Structure

Jenkins, H. Donald Brooke; Pratt, K.F.

doi:10.1016/s0065-2792(08)60079-5

Cited by 46 publications

(9 citation statements)

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“…Bond lengths and atomic partial charges are included on the figure. The IrCl 6 2- bond lengths obtained agree well with the experimental crystallographic value (average bond length = 2.47 Å), and the calculated geometric structure agrees well with a previous calculation 1 Geometric structures (B3LYP/LANL2DZ) of the optimized global minima of (a) the IrCl 6 2- dianion and (b) the IrCl 6 3- trianion.…”

Section: Resultssupporting

confidence: 86%

On the Stability of IrCl₆^3- and Other Triply Charged Anions: Solvent Stabilization versus Ionic Fragmentation and Electron Detachment for the IrCl₆^3-·(H₂O)_n n = 0−10 Microsolvated Clusters

Boxford

Dessent

2005

J. Phys. Chem. A

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The intrinsic gas-phase stability of the IrCl(6)(3-) trianion and its microsolvated clusters, IrCl(6)(3-).(H(2)O)(n) n = 1-10, have been investigated using density functional theory (DFT) calculations. Although IrCl(6)(3-) is known to exist as a stable complex ion in bulk solutions, our calculations indicate that the bare trianion is metastable with respect to decay via both electron detachment and ionic fragmentation. To estimate the lifetime of IrCl(6)(3-), we have computed the electron tunneling probability using an adaption of the Wentzel-Kramer-Brillouin theory and predict that the trianion will decay spontaneously via electron tunneling on a time scale of 2.4 x 10(-13) s. The global minimum structure for IrCl(6)(3-).H(2)O was found to contain a bifurcated hydrogen bond, whereas for IrCl(6)(3-).(H(2)O)(2), two low energy minima were identified; one involving two bifurcated water-ion hydrogen bonds and a second combining a bifurcated hydrogen bond with a water-water hydrogen bond. Clusters based on each of these structural motifs were obtained for all of the n = 3-10 systems, and the effect of solvation on the possible decay pathways was explored. The calculations reveal that solvation stabilizes IrCl(6)(3-) with respect to both electron detachment decay and ionic fragmentation, with the magnitude of the repulsive Coulomb barrier for ionic fragmentation increasing smoothly with sequential solvation. This study is the first to compare the propensity for electron detachment versus ionic fragmentation decay for a sequentially solvated triply charged anion.

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Section: Resultssupporting

confidence: 86%

On the Stability of IrCl₆^3- and Other Triply Charged Anions: Solvent Stabilization versus Ionic Fragmentation and Electron Detachment for the IrCl₆^3-·(H₂O)_n n = 0−10 Microsolvated Clusters

Boxford

Dessent

2005

J. Phys. Chem. A

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“…By performing first principles calculations, Deeth and Jenkins [12] predicted the heterolytic bond enthalpies E(M-X), bond lengths, and energies of hexahalometallate (IV) complexes. The calculated lattice energies are in fair agreement with the data published elsewhere [11]. Another extensive review by Douglas et al [13] focuses on the structure of [MoCl 6 ] 2complexes.…”

supporting

confidence: 84%

“…In these compounds, half metallicity arises due to the strong spin polarization of transition metal dstate and halogens ion p-state [3]. A lot of literature data has been published on the structural properties of this important group of compounds [11][12][13][14][15][16]. However, very limited amount of data is available about the electronic properties of these compounds.…”

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confidence: 99%

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Electronic and magnetic properties of alkali metal chlorides A₂MCl₆ (A = K, Rb, Cs; M = Mn, Mo): A density functional theory study

Faizan

Khan

Murtaza

et al. 2019

Int. J. Mod. Phys. B

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Detailed first-principles calculations of the electronic structure inclusive of magnetic properties of alkali metal chlorides of the type A 2 MCl 6 (A = Alkali metal, M= Mn, Mo) have been performed using the density functional theory (DFT). The calculated optimized lattice constants show close agreement with experimental results. The electronic band structure and density of states were investigated for the first time using different schemes of generalized gradient approximation (GGA) such as Wu-Cohen GGA, modified Becke Johnson potential and GGA plus Hubbard U parameter method. We found that the Hubbard U correction significantly improves the current DFT results. The calculated band structures of K 2 MoCl 6 or Cs 2 MoCl 6 indicate that the spin up electrons have metallic structure while the spin down configurations have semi-conducting nature together resulting in a half-metallic behavior. Finally, the analysis of magnetic properties indicates a ferromagnetic nature for all these compounds. These findings indicate that the alkali metal chlorides K 2 MoCl 6 and Cs 2 MoCl 6 are potentially promising candidates for future applications in the field of spintronics.

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“…Full-Scale Calculations. Historically the calculation/estimation of lattice potential or cohesive energy has been made at varying levels of sophistication − and has been characterized by various milestones. Full scale calculations, needing high level crystal structure data and involving extensive lattice summations, have been made on alkali halides and alkaline earth halide salts, − using a plethora of potentials, some of which are capable of achieving excellent agreement with Born−Fajans−Haber cycle values .…”

Section: Theorymentioning

confidence: 99%

Relationships among Ionic Lattice Energies, Molecular (Formula Unit) Volumes, and Thermochemical Radii

et al. 1999

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The linear generalized equation described in this paper provides a further dimension to the prediction of lattice potential energies/enthalpies of ionic solids. First, it offers an alternative (and often more direct) approach to the well-established Kapustinskii equation (whose capabilities have also recently been extended by our recent provision of an extended set of thermochemical radii). Second, it makes possible the acquisition of lattice energy estimates for salts which, up until now, except for simple 1:1 salts, could not be considered because of lack of crystal structure data. We have generalized Bartlett's correlation for MX (1:1) salts, between the lattice enthalpy and the inverse cube root of the molecular (formula unit) volume, such as to render it applicable across an extended range of ionic salts for the estimation of lattice potential energies. When new salts are synthesized, acquisition of full crystal structure data is not always possible and powder data provides only minimal structural information-unit cell parameters and the number of molecules per cell. In such cases, lack of information about cation-anion distances prevents use of the Kapustinskii equation to predict the lattice energy of the salt. However, our new equation can be employed even when the latter information is not available. As is demonstrated, the approach can be utilized to predict and rationalize the thermochemistry in topical areas of synthetic inorganic chemistry as well as in emerging areas. This is illustrated by accounting for the failure to prepare diiodinetetrachloroaluminum(III), [I(2)(+)][AlCl(4)(-)] and the instability of triiodinetetrafluoroarsenic(III), [I(3)(+)][AsF(6)(-)]. A series of effective close-packing volumes for a range of ions, which will be of interest to chemists, as measures of relative ionic size and which are of use in making our estimates of lattice energies, is generated from our approach.

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Lattice Energies and Thermochemistry of Hexahalometallate(iv) Complexes, A2MX6, Which Possess the Antifluorite Structure

Cited by 46 publications

References 47 publications

On the Stability of IrCl₆^3- and Other Triply Charged Anions: Solvent Stabilization versus Ionic Fragmentation and Electron Detachment for the IrCl₆^3-·(H₂O)_n n = 0−10 Microsolvated Clusters

On the Stability of IrCl₆^3- and Other Triply Charged Anions: Solvent Stabilization versus Ionic Fragmentation and Electron Detachment for the IrCl₆^3-·(H₂O)_n n = 0−10 Microsolvated Clusters

Electronic and magnetic properties of alkali metal chlorides A₂MCl₆ (A = K, Rb, Cs; M = Mn, Mo): A density functional theory study

Relationships among Ionic Lattice Energies, Molecular (Formula Unit) Volumes, and Thermochemical Radii

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Lattice Energies and Thermochemistry of Hexahalometallate(iv) Complexes, A2MX6, Which Possess the Antifluorite Structure

Cited by 46 publications

References 47 publications

On the Stability of IrCl63- and Other Triply Charged Anions: Solvent Stabilization versus Ionic Fragmentation and Electron Detachment for the IrCl63-·(H2O)n n = 0−10 Microsolvated Clusters

On the Stability of IrCl63- and Other Triply Charged Anions: Solvent Stabilization versus Ionic Fragmentation and Electron Detachment for the IrCl63-·(H2O)n n = 0−10 Microsolvated Clusters

Electronic and magnetic properties of alkali metal chlorides A2MCl6 (A = K, Rb, Cs; M = Mn, Mo): A density functional theory study

Relationships among Ionic Lattice Energies, Molecular (Formula Unit) Volumes, and Thermochemical Radii

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On the Stability of IrCl₆^3- and Other Triply Charged Anions: Solvent Stabilization versus Ionic Fragmentation and Electron Detachment for the IrCl₆^3-·(H₂O)_n n = 0−10 Microsolvated Clusters

On the Stability of IrCl₆^3- and Other Triply Charged Anions: Solvent Stabilization versus Ionic Fragmentation and Electron Detachment for the IrCl₆^3-·(H₂O)_n n = 0−10 Microsolvated Clusters

Electronic and magnetic properties of alkali metal chlorides A₂MCl₆ (A = K, Rb, Cs; M = Mn, Mo): A density functional theory study