Bond anisotropy order

K, the static disorder is certainly maintained. The results are presented as plots of formula in Fig. 7. The deviations from linearity of the plots is small enough to support such method of analysis. The slopes of the curves give the 5a values tabulated in Table 4. It follows that in the (1 x l)Co/Cu(lll) case the anisotropy of surface vibrations clearly appears in the measured values of 8a and 5aT There are two reasons for such anisotropy the first is a surface effect due to the reduced coordination in the perpendicular direction. cF is a mean-square relative displacement projected along the direction of the bond Enhanced perpendicular vibrational amplitude causes enhanced mean-square relative displacement along the S—B direction. The second effect is due to the chemical difference of the substrate (Fig. 8). S—B bonds are Co—Cu bonds and the bulk Co mean-square relative displacement, cr (Co), is smaller than the bulk value for Cu, aJ(Cu). Thus for individual cobalt-copper bonds, the following ordering is expected ... 

This picture can qualitatively account for the g tensor anisotropy of nitrosyl complexes in which g = 2.08, gy = 2.01, and g == 2.00. However, gy is often less than 2 and is as small as 1.95 in proteins such as horseradish peroxidase. To explain the reduction in g from the free electron value along the y axis, it is necessary to postulate delocalization of the electron over the molecule. This can best be done by a complete molecular orbital description, but it is instructive to consider the formation of bonding and antibonding orbitals with dy character from the metal orbital and a p orbital from the nitrogen. The filled orbital would then contribute positively to the g value while admixture of the empty orbital would decrease the g value. Thus, the value of gy could be quite variable. The delocalization of the electron into ligand orbitals reduces the occupancy of the metal d/ orbital. This effectively reduces the coefficients of the wavefunction components which account for the g tensor anisotropy hence, the anisotropy is an order of magnitude less than might be expected for a pure ionic d complex in which the unpaired electron resides in the orbital. 

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