Magnetic coupling orbital

The application of these rules may fail for the prediction of magnetic coupling in transition-metal clusters, where the molecular orbitals may be different from simple atomic d-orbitals and a simple ligand field analysis may not reflect the correct energy splittings. 

In the absence of an external magnetic field, orbitally nondegenerate levels with spin multiplicity greater than 2 split due to direct electron spin—spin coupling (in first order) and spin—orbit coupling (in second and higher orders of perturbation theory). This phenomenon is called zero-field splitting (ZFS). The SH that describes this phenomenon can be formulated in... 

The Cua site, common in biology (inset in Fig. 5.42), is dinuclear with two copper atoms bridged by the thiolate sulfurs of two cysteine ligands. One unpaired electron is delocalized over two metals, which are thus Cul 5+. The NMR spectra show narrow lines from the copper ligands (Fig. 5.42) [120,121], corresponding to an electron relaxation time of 10 11 s, as in Cu2+-Cu2+ dimers (see Section 6.3.2). However, in Cua there is no magnetic coupling between the two centers, as they contain only one unpaired electron just as an isolated Cu2+ ion. Electron relaxation of Cua may be fast because the orbital overlap between the two copper centers provides new relaxation mechanisms not available to a monomer (as Orbach or Raman relaxation). 

There are no treatments for the pseudocontact term, since the orbital part has never been considered when dealing with magnetic coupled systems. However, Eqs. (6.7) and (6.10) hold for the hyperfine splitting in EPR spectra of both solids and solutions [1]. Therefore the same reasoning is likely to apply to the pseudocontact shift as well. The major complication arises from the point-dipolar nature of the pseudocontact shift treatment, which contrasts with the idea of a polymetallic center. 

TABLE 3 CASSCF and CASPT2 values of the magnetic coupling parameter J (in meV) for bulk TMO and fartheTMO (100) surface. The active space in the CASSCF is Formed by the open shell orbitals located on the I M ions and the unpaired electrons. CASPT2 correlates the TM-3s, 3p. 3d and die 0-2s, 2p electrons... 

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