Multiplet excitations

Fig. 10. Raman spectra of the series CejSj, CejS and CeS at lOK. Of particular interest are the CEF-split 7-multiplet excitations above 2000 cm , after Morke et al. (1986).

In the early 1990s, a new spin polarization mechanism was posPilated by Paul and co-workers to explain how polarization can be developed m transient radicals in the presence of excited triplet state molecules (Blattler et al [43], Blattler and Paul [44], Goudsmit et al [45]). While the earliest examples of the radical-triplet pair mechanism (RTPM) mvolved emissive polarizations similar in appearance to triplet mechanism polarizations, cases have since been discovered m which absorptive and multiplet polarizations are also generated by RTPM. 

We further make the following tentative conjecture (probably valid only under restricted circumstances, e.g., minimal coupling between degrees of freedom) In quantum field theories, too, the YM residual fields, A and F, arise because the particle states are truncated (e.g., the proton-neutron multiplet is an isotopic doublet, without consideration of excited states). Then, it is within the truncated set that the residual fields reinstate the neglected part of the interaction. If all states were considered, then eigenstates of the form shown in Eq. (90) would be exact and there would be no need for the residual interaction negotiated by A and F. 

The ground configuration of Ar is KL3s 3p, giving an inverted P /2 multiplet. The excited states involved in laser action involve promotion of an electron from the 3p orbital into excited As,5s,Ap,5p,3d,Ad,... orbitals. Similarly, excited states of Kr involved arise from promotion of an electron from the Ap orbital. In Ar the KL3s 3p configuration gives rise to 5, V, terms (see Section 7.1.2.3). Most laser transitions involve the core in one of the states and the promoted electron in the Ap orbital. 

Decoupling has two effects all multiplets are coUapsed into singlets, one for each nonequivalent atom and the transfer of NOE from the excited H to... 

A homonuclear spin-system may be excited with radiofrequency (r.f.) pulses that are so Intense (in the order of p.s), compared to the frequency width of the spectrum, that all resonances are excited essentially uniformly. This is a nonselective excitation. A homonuclear spin-system may also be excited with a relatively weak, r.f. pulse (in the order of ms), in the sense that all components of a given multiplet are inverted at time zero, whereas the other resonances in the spectrum remain essentially unperturbed this is a selective excitation. The r.f. pulse may be single-selective, that is, there is an inversion of one multiplet in the spectrum, or double-selective, triple-selective, and so on, where two, three, or more separate multiplets in the spectrum are inverted simultaneously while the remaining resonances remain unperturbed. 

Figure 7.1 Selective excitation of only one multiplet by a selective pulse transforms a 2D experiment into a ID technique. A selective pulse generates the transverse magnetization. The result is a trace of the corresponding 2D spectrum. (Reprinted from Mag. Reson. Chem. 29, H. Kessler ei al., 527, copyright (1991), with permission from John Wiley and Sons Limited, Baffins Lane, Chichester, Sussex P019 lUD, England.)...

A 90° Gaussian pulse is employed as an excitation pulse. In the case of a simple AX spin system, the delay t between the first, soft 90° excitation pulse and the final, hard 90° detection pulse is adjusted to correspond to the coupling constant JJ x (Fig- 7.2). If the excitation frequency corresponds to the chemical shift frequency of nucleus A, then the doublet of nucleus A will disappear and the total transfer of magnetization to nucleus X will produce an antiphase doublet (Fig. 7.3). The antiphase structure of the multiplets can be removed by employing a refocused ID COSY experiment (Hore, 1983). 

Soft-pulse multiple irradiation In this method, pre-saturation is done using shaped pulses having a broader excitation profile. Therefore, it is a more suitable method for the suppression of multiplets. This technique is very effective, easy to apply and easy to implement within most NMR experiments. In aqueous solutions, however, slowly exchanging protons would be detectable due to the occurrence of transfer of saturation. In addition, the spins with resonances close to the solvent frequency will also be saturated. 

The first attempts to rationalize the magnetic properties of rare earth compounds date back to Hund [10], who analysed the magnetic moment observed at room temperature in the framework of the old quantum theory, finding a remarkable agreement with predictions, except for Eu3+ and Sm3+ compounds. The inclusion by Laporte [11] of the contribution of excited multiplets for these ions did not provide the correct estimate of the magnetic properties at room temperature, and it was not until Van Vleck [12] introduced second-order effects that agreement could be obtained also for these two ions. 

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