By Malcolm Gerloch, Edwin C. Constable
By means of advantage of its non-mathematical and strongly visible method of bonding, it offers a so much available textual content at the diverse nature of the valence shell in d-block chemistry. Paper.
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Once more, orbital energies are indicated with respect to a barycentre rule. 11) and the trio lies higher in energy than the pair. The d orbital subsets are labelled t2 and e. 6 Atet or - 6Dq Figure 3-7. Barycentre splitting of d orbitals in tetrahedral symmetry. 34 3 Crystal-Field Splittings Note the absence of the g subscripts here. Although the d orbitals are still centrosymmetric, the tetrahedral environment lacks a centre of inversion. e. u (ungerade or odd). Overall, then, we observe that the orbitals are inversely split in the tetrahedron with respect to the octahedron.
Recall our caveat when asserting 3 3 that the relative energy of the Γ1§ (from t2g) and the A 2g (from e%) is not given simply by Aoci, the energy splitting of the t2g and eg orbitals. That is because the electron - electron repulsion energies for these two arrangements are not the same. They are not the same because the spatial proximity of members of the eg orbital pair is not the same as that for members of the t2g set. Similarly, the proximities and interelectron repulsion energies vary within the electronic arrangements of the t2geg configuration, as we now discuss.
More will be said about such term symbols in the next two sections. 38 3 Crystal-Field Splittings Box 3-5 Again the left superscript indicates the spin-triplet nature of the arrangement. The letter A means that it is spatially (orbitally) one-fold degenerate and it is upper-case because we describe two-electron wavefunctions. The subscript is g because the product of d orbitals is even under the octahedral centre of inversion, and the right subscript 2 must remain a mystery for us once again. have fixed that as spin-parallel), there is only one way of filling this orbital subset.