Ab initio investigations of the electronic structures and chemical bonding in LiCo6P4 and Li2Co12P7

Zeitschrift anorg allge chemie

2014

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Selected ternary compounds of the family of AT 6 X 4 (LiCo 6 P 4 -type) intermetallics were studied by ab initio methods with respect to their electronic structures and chemical bonding. The bonding characteristics highlight the role of the three-dimensional [T 6 X 4 ] polyanionic networks which, within the hexagonal channels, accommodate loosely bonded A cations. In alkali metal based compounds, * Dr. S. F. Matar 1641 when T is replaced by indium (e.g. in KIn 6 Au 4 ) the reverse occupancy leads to positively charged In (ca. +0.5) and negatively charged Au (ca. -0.9). Peculiar magnetic behavior is traced out whereby a magnetic order is identified only when T is a 3d element, which polarizes and induces a negative small moment on A (U) as in UCr 6 P 4 oppositely to CeRh 6 X 4 for X = Si, Ge.

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 92%

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The Family of LiCo₆P₄ Type Compounds – Trends in Electronic Structure and Chemical Bonding

Matar

Zeitschrift anorg allge chemie

2014

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“…Thus, extensive metal-metal bonding stabilizes these structures as well. This is underlined by recent ab initio investigations on the electronic structure and chemical bonding (Matar et al 2013).…”

Section: Structural Chemistrymentioning

confidence: 92%

“…Also, in LiP 7 (von Schnering and Wichelhaus 1972), the Li-P distances range from 267 to 288 pm, but with distorted octahedral coordination. Total energy calculations indicate stability of the delithiated substructures (Matar et al 2013).…”

Section: Structural Chemistrymentioning

confidence: 99%

Lithium transition metal pnictides – structural chemistry, electrochemistry, and function

Winter

Reviews in Inorganic Chemistry

Greiwe

et al. 2014

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Lithium-transition metal (T)-pnictides (Pn = P, As, Sb, Bi) are an interesting class of materials with greatly differing crystal structures. The transition metal and pnictide atoms build up covalently bonded networks that leave cavities or channels for the lithium atoms. Depending on the bonding of lithium to the polyanionic network, one observes mobility of the lithium atoms. The crystal chemistry, chemical bonding, 7 Li solid-state NMR, and the electrochemical behavior of the pnictides are reviewed. The structural chemistry is compared with related tetrelides.

Rhodium-rich silicides RERh₆Si₄ (RE=La, Nd, Tb, Dy, Er, Yb)

Voßwinkel

Zeitschrift Für Naturforschung B

2017

Polycrystalline RERh6Si4 (RE=La, Nd, Tb, Dy, Er, Yb) samples can be synthesized by arc-melting of the elements. Single crystals of LaRh6Si4, NdRh6Si4 and YbRh6Si4 were synthesized from the elements in bismuth fluxes (non-reactive flux medium). The structures were refined on the basis of single-crystal X-ray diffractometer data: LiCo6P4 type, P6̅m2, a=700.56(3), c=380.55(1) pm, wR2=0.0257, 317 F2 values, 19 variables for LaRh6Si4, a=698.4(5), c=377.7(2) pm, wR2=0.0578, 219 F2 values, 19 variables for NdRh6Si4 and a=696.00(3), c=371.97(1) pm, wR2=0.0440, 309 F2 values, 19 variables for YbRh6Si4. The rhodium and silicon atoms build up three-dimensional, covalently bonded [Rh6Si4]δ− polyanionic networks with Rh–Si distances ranging from 239 to 249 pm. The rare earth atoms fill larger cavities within channels of these networks and they are coordinated by six silicon and twelve rhodium atoms in the form of hexa-capped hexagonal prisms.