Electron Zeeman

The transition between levels coupled by the oscillating magnetic field B corresponds to the absorption of the energy required to reorient the electron magnetic moment in a magnetic field. EPR measurements are a study of the transitions between electronic Zeeman levels with A = 1 (the selection rule for EPR). 

The coupling constants of the hyperfme and the electron Zeeman interactions are scalar as long as radicals in isotropic solution are considered, leading to the Hamiltonian... 

The first temi describes the electronic Zeeman energy, which is the interaction of the magnetic field with the two electrons of the radical pair with the magnetic field, Bq. The two electron spins are represented by spin... 

OIDEP usually results from Tq-S mixing in radical pairs, although T i-S mixing has also been considered (Atkins et al., 1971, 1973). The time development of electron-spin state populations is a function of the electron Zeeman interaction, the electron-nuclear hyperfine interaction, the electron-electron exchange interaction, together with spin-rotational and orientation dependent terms (Pedersen and Freed, 1972). Electron spin lattice relaxation Ti = 10 to 10 sec) is normally slower than the polarizing process. 

Energy level splitting in a magnetic field is called the Zeeman effect, and the Hamiltonian of eqn (1.1) is sometimes referred to as the electron Zeeman Hamiltonian. Technically, the energy of a... 

The spin Hamiltonian for a biradical consists of terms representing the electron Zeeman interaction, the exchange coupling of the two electron spins, and hyperfine interaction of each electron with the nuclear spins. We assume that there are two equivalent nuclei, each strongly coupled to one electron and essentially uncoupled to the other. The spin Hamiltonian is ... 

We now notice that we could write a Hamiltonian operator that would give the same matrix elements we have here, but as a first-order result. Including the electron Zeeman interaction term, we have the resulting spin Hamiltonian ... 

We have seen in Chapter 2 that the electronic Zeeman term, the interaction between unpaired electrons in molecules and an external magnetic field, is the basis of EPR, but we have also discussed in Chapter 4 the fact that if a system has more than one unpaired electron, their spins can mutually interact even in the absence of an external field, and we have alluded to the fact that this zero-field interaction affords EPR spectra that are quite different from those caused by the Zeeman term alone. Let us now broaden our view to include many more possible interactions, but at the same time let us be systematic and realize that this plethora of possibilities is eventually reducible to five basic types only, two of which are usually so weak that they can be ignored. 

By far the most important influence of a nuclear spin on the EPR spectrum is through the interaction between the electron spin S and the nuclear spin I. Usually, at X-band frequencies this interaction is weaker, by an order of magnitude or more, than the electronic Zeeman interaction, and so it introduces small changes in the EPR spectrum known as hyperfine structure. As a first orientation to these patterns, note that just like the electron spin S, also the nuclear spin / has a multiplicity ... 

Before we develop the resonance conditions for systems with hyperhne and with zero-held interactions, we return to the electronic Zeeman term S B as an example interaction to discuss a hitherto ignored complexity that is key to the usefulness of EPR spectroscopy in (bio)chemistry, namely anisotropy the fact that all interactions... 

FIGURE 5.2 A schematic model of multiple X Y interactions. Black dots are unpaired electrons the central, big black dot is the point of EPR observation. Straight lines are interactions a single straight line symbolizes the electronic Zeeman interaction S B double lines represent central and ligand hyperfine interactions S I triple lines are zero-field interactions S S between electrons (i) around a single metal (ii) at different centers within a molecule and (iii) at centers in different molecules. 

Now we can define the anisotropic resonance condition for an S = 1/2 system subject to the electronic Zeeman interaction only as... 

Suppose we have an isolated system with a single unpaired electron and no hyper-fine interaction. Mononuclear low-spin Fe111 and many iron-sulfur clusters fall in this category (cf. Table 4.2). The only relevant interaction is the electronic Zeeman term, so the spin Hamiltonian is... 

Systems with more than one unpaired electron are not only subject to the electronic Zeeman interaction but also to the magnetic-field independent interelectronic zero-field interaction, and the spin Hamiltonian then becomes... 

For biomolecular S = 1/2 systems subject to central hyperfine interaction the intermediate-field situation (B S S I) is not likely to occur unless the micro-wave frequency is lowered to L-band values. When v = 1 GHz, the resonance field for g = 2 is at B = 357 gauss. Some Cu(II) sites in proteins have Az 200 gauss, and this would certainly define L-band EPR as a situation in which the electronic Zeeman interaction is comparable in strength to that of the copper hyperfine interaction. No relevant literature appears to be available on the subject. An early measurement of the Cun(H20)6 reference system (cf. Figure 3.4) in L-band, and its simulation using the axial form of Equation 5.18 indicated that for this system... 

An—at least, theoretically—simple example is the S = 1 system in weak-field subject to a dominant zero-field interaction and a weakly perturbing electronic Zeeman interaction (similar to the S = 2 case treated above). The initial basis set is... 

We can now extend the spin Hamiltonians by making combinations of T, with B, and/or S, and/or I, and since we are interested in the effect of strain on the g-value from the electronic Zeeman interaction (B S), the combination of interest here is T B S. 

The spin Hamiltonian encompassing electronic Zeeman plus strain interaction for a cubic S = 1/2 system is (Pake and Estle 1973 Equation 7-21) ... 

Note that the Zeeman interaction for a cubic system results in an isotropic g-value, but the combination with strain lowers the symmetry at least to axial (at least one of the 7 -, 0), and generally to rhombic. In other words, application of a general strain to a cubic system produces a symmetry identical to the one underlying a Zeeman interaction with three different g-values. In yet other words, a simple S = 1/2 system subject to a rhombic electronic Zeeman interaction only, can formally be described as a cubic system deformed by strain. 

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