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What do kinetic‐energy anisotropies tell us about chemical bonding? I. Diatomic hydrides
Author(s) -
Sharma B. S.,
Thakkar Ajit J.
Publication year - 1986
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.560290306
Subject(s) - diatomic molecule , kinetic energy , anisotropy , chemistry , atomic orbital , chemical bond , dimensionless quantity , atomic physics , atom (system on chip) , bond energy , computational chemistry , thermodynamics , physics , electron , quantum mechanics , molecule , organic chemistry , computer science , embedded system
The kinetic‐energy anisotropies of fifteen diatomic hydrides AH with A = H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl are calculated from self‐consistent‐field wave functions constructed from extended basis sets of Slater‐type orbitals. It is found that there is no consistent ordering of the bond‐parallel and bond‐perpendicular components of the kinetic energy with respect to separated atom values. An analysis of the orbital contributions reveals that nonbonding π orbitals make large contributions to the total kinetic‐energy anisotropy. This makes it difficult, if not impossible, to deduce anything about the nature of the chemical bond from the total anisotropy. However, certain dimensionless orbital kinetic‐energy anisotropies are useful for interpretative studies because, in free atoms, these quantities have fixed values that depend only on the symmetry of the orbital.