Triple electron spin resonance

The data on electron spin resonance (ESR), electron-nuclear double resonance (ENDOR), and general triple resonance spectroscopy for 2,5-dihydro-l,2,3,5-thiatriazole-5-yl radicals was reviewed by Holm and Larsen <1996CHEC-II(4)733>. There are no new data on this subject. 

J. C. Evans, A. G. Evans, N. H. Nouri-Sorkhabi, A. Y. Obaid, and C. C. Rowlands, An electron spin resonance, ENDOR, and TRIPLE resonance study of methyl-substituted AGV-diphenyl-4,4-bipyridylium dichloride radical cations,./. Chem. Soc., Perkin Trans. 2 1985, 315-318. 

The iminoxyl radical observed by electron spin resonance (ESR) proves the formation of ketocarbene in the process of triple-bond oxidation by NO under the action of visible light. 

There are many other specialized methods electron-electron double resonance (ELDOR), TRIPLE, HYSCORE (hyperfine sublevel correlation spectroscopy, which is similar to 2D-EPR), electron spin-echo, and so on these methods are not discussed here. 

The sign of Ajso is an indicator of the origin of the mechanism that introduces the j-orbital spin density. The standard ENDOR experiment does not yield the sign of A, but advanced techniques such as TRIPLE (electron-nuclear-nuclear triple resonance) do provide this information. 

Abstract Multi-resonance involves ENDOR, TRIPLE and ELDOR in continuous-wave (CW) and pulsed modes. ENDOR is mainly used to increase the spectral resolution of weak hyperfine couplings (hfc). TRIPLE provides a method to determine the signs of the hfc. The ELDOR method uses two microwave (MW) frequencies to obtain distances between specific spin-labeled sites in pulsed experiments, PELDOR or DEER. The electron-spin-echo (ESE) technique involves radiation with two or more MW pulses. The electron-spin-echo-envelope-modulation (ESEEM) method is particularly used to resolve weak anisotropic hfc in disordered solids. HYSCORE (Hyperfine Sublevel Correlation Spectroscopy) is the most common two-dimensional ESEEM method to measure weak hfc after Fourier transformation of the echo decay signal. The ESEEM and HYSCORE methods are not applicable to liquid samples, in which case the FID (free induction decay) method finds some use. Pulsed ESR is also used to measure magnetic relaxation in a more direct way than with CW ESR. 

In part the interest arises from the fact that the spectroscopic state 87/2 is the same for the atom, 4f 6s as for the divalent ion, 4f . The former has been studied by atomic beam triple resonance (Sandars and Woodgate 1960, Evans et al. 1965), and the latter by ENDOR (Baker and Williams 1962) in Cap2, an environment with cubic symmetry. For a half-filled shell, with no orbital momentum and a spherical distribution of electron spin moment with zero density at the nucleus, both the magnetic dipole and electric quadrupole interactions should be zero. Experimentally, they are small compared with the values for other odd-proton lanthanide isotopes with comparable nuclear moments, for which the hyperfine... 

There are many experimental techniques for the determination of the Spin-Hamiltonian parameters g, Ux, J. D, E. Often applied are Electron Paramagnetic or Spin Resonance (EPR, ESR), Electron Nuclear Double Resonance (ENDOR) or Triple Resonance, Electron-Electron Double Resonance (ELDOR), Nuclear Magnetic Resonance (NMR), occasionally utilizing effects of Chemically Induced Dynamic Nuclear Polarization (CIDNP), Optical Detections of Magnetic Resonance (ODMR) or Microwave Optical Double Resonance (MODR), Laser Magnetic Resonance (LMR), Atomic Beam Spectroscopy, and Muon Spin Rotation (/iSR). The extraction of data from the spectra varies with the methods, the system studied and the physical state of the sample (gas, liquid, unordered or ordered solid). For these procedures the reader is referred to the monographs (D). Further, effective magnetic moments of free radicals are often obtained from static... 

In conclusion, although it has been demonstrated that a three-spin effect exists, it is usually unimportant unless the radical concentration is low. This is readily understandable, since the magnetic moment of the electron is much larger than that of any nucleus so that nuclear-electron interactions are the dominant relaxation terms, except at low concentrations where nuclear—nuclear interactions become important. The presence of a three-spin effect can be revealed most easily either by observation of the transient relaxation behaviour of the nuclear resonance or by triple irradiation experiments. In the latter case, account must be taken of the collapse of any multiplet structure in the interpretation of the results. 

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