Absorption Spectra and Chemical Bonding in Complexes by C. K. Jorgensen

By C. K. Jorgensen

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The corresponding values can be approximately extrapolated in the 6+ 6+ gaseous ions to increase from 4 kK in R e to some 10 kK for P t . The decrease of £5d is less accentuated than that of the interelectronic repulsion parameters to be discussed in the section on the nephelauxetic series (the ratio being 0-47 for OsF 6, 0-38 for IrF 6, and 0-30 for PtF 6). Some values are compiled in Table 9, p. 84. As will be discussed in Chapter 10, the effects of large ζ ηρ are even more conspicuous in the series T1(I), Pb(II), Bi(III), having 2 transitions which in the gaseous ions would be 6s -> 6s6p, and in the electron transfer spectra of halide complexes, where in the gaseous atoms £ np is strongly increasing with Ζ (eqn.

FIG. 2. The co-ordinate system to be used for octahedral complexes. One ρ and two d orbitals of the central atom M are indicated, and also two of the linear combinations of the ligands' orbitals from Table 4. The - f and — indicate the signs of the one-electron wave functions. Ten values of Γη are possible in the cubic-octahedral symmetry. The parity is even or odd and combined with one of five values, for which Mulliken has proposed other names, according to their degeneracy number e: Bethe: Γλ Mulliken: Α1 e = 1 Γ2 Α2 1 Γ3 Ε 2 Γ4 Τχ 3 Γ5 Τ2 3 (43) and the orbitals have the analogous names y n (or a 1?

There is a fundamental difference between the non-diagonal elements of eqn. (28) and eqn. (29). The former always subsist, even with the best choice of the orbitals, while the latter actually behave almost as one-electron operator quantities, ("mixk k ing" the orbitals a and b ) and are negligible if the orbitals are selfconsistent. In the next chapter we will discuss how the concept of effective microsymmetry is important to the question of whether the energy differences between a set of nearly degenerate molecular orbitals are sufficiently larger than the parameters of interelectronic repulsion to secure a sound basis for the classification according to configurations.

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