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Determination of the charge distribution in nonmetallic crystals. I. Theory and application to tetrahedrally coordinated solids
Author(s) -
Julg André,
Marinelli Francis,
Pellégatti Alain
Publication year - 1978
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560140206
Subject(s) - polarizability , electronegativity , atomic orbital , linear combination of atomic orbitals , wurtzite crystal structure , chemistry , madelung constant , formalism (music) , localized molecular orbitals , basis set , computational chemistry , molecular physics , quantum mechanics , physics , crystal structure , crystallography , molecule , electron , density functional theory , hexagonal crystal system , lattice energy , art , musical , visual arts
A SCF method using localized molecular orbitals which are built up on hybrid atomic orbitals is proposed to obtain the charges in infinite crystals. Hybrid orbitals are built up on a minimal STO basis set. The formalism has been adapted in order to take into account the periodicity of the system and its infinite size by introducing the Madelung constant. The total energy is given by an infinite sum of terms each corresponding to the energy of a bond in the crystal field. Minimizing this bond energy with respect to eigenvectors it is straightforward to obtain the electronic charges, whence the polarity, i.e., the ionicity, of bonds. In this first paper, we study and discuss the polarity of bonds in zincblende and wurtzite‐type compounds built up on first and second row elements. Our values are coherent between themselves and in agreement with other authors' results. The connection with electronegativity and polarizability is discussed.