ISSN:
1432-2234
Keywords:
Valence-bond
;
Water
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract Minimal Slater basis set valence-bond calculations on the1 A 1 ground state of H2O are reported. Determinants built up from both natural and hybrid orbitals were used. The calculations were performed at $$\widehat{{\text{HOH}}}$$ bond angles of 90 °, 95 °, 100 °, 105 ° and 120 °. The most important natural atomic configuration is 1s 22s 22p x u2 2p y2p z h 1 h 2. The relative importance of the various natural atomic configurations was determined by examining configuration energies, position in a build-up study and coefficient in a “full” valence-bond wavefunction. The molecular orbital and “full” valence-bond wavefunctions were compared. The perfect pairing calculations using a set of orthogonal hybrid orbitals suggest that the bonding orbitals exhibit a “non-perfect following” behaviour as the molecule bends, continuing to point approximately in their equilibrium directions. The optimum bonding hybrid orbitals are almost pure 2p orbitals and the lone-pair orbitals 2s-2p hybrids, although a small hybridization of the bonding hybrids is essential to obtain an accurate description of the geometry.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00578226
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