Theoretical investigation of the stability and structure of the complex hydrides LBH/sub 4/ and LiMH/sub 4/ (L = Li, Na, K, and Cu; M = B, Al, and Sc)
Nonempirical calculations of the most interesting portions of the potential surfaces in the vicinity of the mono- (m), bi- (b), and tridentate (t) configurations of the KBH/sub 4/, CuBH/sub 4/, and LiScH/sub 4/ molecules have been carried out with the use of several double-zeta basis sets. In all cases, the b and t configurations are close in energy (the difference does not exceed 16 kJ), and the m configuration is 63-84 kJ higher and is clearly less advantageous. In the case of KBH/sub 4/, the t configuration is most advantageous, in the case of CuBH/sub 4/, the b configuration is most advantageous, and in the case of LiScH/sub 4/, the b and t configurations are practically degenerate with respect to their energies. It has been concluded that all these complex salts are flexible with respect to migration of the outer-sphere cation around the tetrahedral MH/sub 4//sup -/ anion along the path b ..-->.. t ..-->.. b' ..-->.. t' ..-->.. ... The results have been compared with the data from the preceding calculations of the potential surfaces of the LiBH/sub 4/, NaBH/sub 4/, and LiAlH/sub 4/ molecules. The influence of the cation L/sup +/ and the central atom M in the MH/sub 4//sup -/ anion on the form of the potential surface, the relative energy, and the structures of the alternative configurations, as well as the stability with respect to the dissociation processes LMH/sub 4/ ..-->.. LH + MH/sub 3/ and LMH/sub 4/ ..-->.. L..mu.. + MH/sub 4//sup -/, has been analyzed in series of complex hydrides such as LiBH/sub 4/-NaBH/sub 4/-KBH/sub 4/-CuBH/sub 4/ and LiBH/sub 4/-LiAlH/sub 4/-LiScH/sub 4/.
- Research Organization:
- M.V. Lomonosov Moscow Institute of Fine Chemical Technology, USSR
- OSTI ID:
- 6509285
- Journal Information:
- Sov. J. Coordinat. Chem.; (United States), Journal Name: Sov. J. Coordinat. Chem.; (United States) Vol. 11:6; ISSN SJCCD
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
653001 -- Nuclear Theory-- Nuclear Structure
Moments
Spin
& Models
73 NUCLEAR PHYSICS AND RADIATION PHYSICS
ALKALI METAL COMPOUNDS
ALUMINIUM COMPOUNDS
ALUMINIUM HYDRIDES
ATOMIC MODELS
BORON COMPOUNDS
BORON HYDRIDES
CATIONS
CHARGED PARTICLES
CONFIGURATION INTERACTION
COORDINATION VALENCES
COPPER COMPOUNDS
COPPER HYDRIDES
DEFORMATION
DEFORMED NUCLEI
DISSOCIATION HEAT
DISTANCE
ELECTRONIC STRUCTURE
ENTHALPY
HYDRIDES
HYDROGEN COMPOUNDS
INTERATOMIC DISTANCES
IONS
LIGANDS
LITHIUM COMPOUNDS
LITHIUM HYDRIDES
MATHEMATICAL MODELS
MOLECULAR STRUCTURE
NUCLEAR CORES
NUCLEAR DEFORMATION
NUCLEI
ORIENTATION
PHYSICAL PROPERTIES
POTASSIUM COMPOUNDS
POTASSIUM HYDRIDES
REACTION HEAT
SCANDIUM COMPOUNDS
SCANDIUM HYDRIDES
SODIUM COMPOUNDS
SODIUM HYDRIDES
SPIN ORIENTATION
STRUCTURAL CHEMICAL ANALYSIS
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPOUNDS
VALENCE