Spin-orbit coupling constant, value

Table 24. Free-ion spin-orbit coupling constant values ...

Figure A The variation with temperature and spin-orbit coupling constant, of the magnetic moments of octahedral, low-spin, d" ions, (The values of at 300 K are marked for individual ions).

Fig. 2. Temperature dependence of the HS fraction % according to the Ising model. The employed parameter values are = 150 K, Aj = Aj = 500 cm and X = — 100 em h Here, Aj and Aj are the orbital energy differences between the and levels and between the Bj and levels, respectively, X being the spin-orbit coupling constant. The model parameters A, Aj, and X determine the value of AG. The levels result from the HS iron(II) ground state in orthorhombic symmetry according to Bj -1- B2 + B. The figures on the curves specify the values of...

Here, L is the angular momentum operator, ge is the g value for the free electron (ge = 2.0023), and X is the spin-orbit coupling constant. Considering only the z direction, this equation becomes... 

We have though previously expressed our reservations (10, 11) concerning the combination of ft and ft data for the derivation of a2 and (ZjZ0). Thus, whereas the repulsion parameter, B, is essentially an outer radial quantity (82, 83) the spin-orbit coupling constant, , is dominantly an inner orbital function (84). Moreover the (ZjZo) values derived in most cases indicate a rather small measure of central field covalency. Nevertheless, the a2 values obtained tend to parallel the mm rather than the a 0ot values, especially as the extent of covalency increases from the M(IV) to M(V) to M(VI) series, thus suggesting that flroot values may be too large. On the other hand the values are likely... 

We have not as yet however treated the charge-transfer data available for complexes of the 5 d series. For these latter species though the effective spin-orbit coupling constants are often of the order of 3 kK. or more, as compared with only about 1 kK. for Ad systems, and smaller values still for the 3d elements. Consequently, as for the d—d transitions it is often necessary explicitly to consider relativistic effects in the interpretation of charge-transfer spectra, and in particular to make allowance for the changes in spin-orbit contributions which may accompany a given di transition. In fact one of us has shown (18) that these changes are... 

The ligand field was parameterised in terms of ea only, and values of this parameter, together with the spin-orbit coupling constant X, the orbital reduction factor k and the Racah parameter B were obtained by fitting the d-d spectra, zero-field splittings, principal magnetic susceptibilities and e.s.r. g-values. 

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