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Hyperfine coupling spectroscopy

Kasai and McLeod (57, 58) also studied a series of bimetallic diatomics, AgM (M = Mg, Ca, Sr, Be, Zn, Cd, or Hg), by ESR spectroscopy. For all of these species, the hyperfine coupling to the Ag nucleus was found to be isotropic. It was shown that the unpaired electron resides in an orbital resulting essentially from an anti-bonding combination of the valence s orbitals of the Ag and M atoms. A typical spectrum is shown in Fig. 13. [Pg.100]

Hyperfine Coupling Values of the Nitrogen Ligands of Rieske and Rieske-Type Clusters Determined by ENDOR and ESEEM Spectroscopy... [Pg.133]

When several magnetically equivalent nuclei are present in a radical, some of the multiplet lines appear at exactly the same field position, i.e., are degenerate , resulting in variations in component intensity. Equivalent spin-1/2 nuclei such as 1H, 19F, or 31P result in multiplets with intensities given by binomial coefficients (1 1 for one nucleus, 1 2 1 for two, 1 3 3 1 for three, 1 4 6 4 1 for four, etc.). One of the first aromatic organic radical anions studied by ESR spectroscopy was the naphthalene anion radical,1 the spectrum of which is shown in Figure 2.2. The spectrum consists of 25 lines, a quintet of quintets as expected for hyperfine coupling to two sets of four equivalent protons. [Pg.22]

Several thiadiazole-fused organic radicals have been characterized by ESR spectroscopy, and significant spin delocalization can be seen from the hyperfine coupling constants (hfcc s) N (Table 5). [Pg.523]

Since the phenoxyls possess an S = ground state, they have been carefully studied by electron paramagnetic spectroscopy (EPR) and related techniques such as electron nuclear double resonance (ENDOR), and electron spin-echo envelope modulation (ESEEM). These powerful and very sensitive techniques are ideally suited to study the occurrence of tyrosyl radicals in a protein matrix (1, 27-30). Careful analysis of the experimental data (hyperfine coupling constants) provides experimental spin densities at a high level of precision and, in addition, the positions of these tyrosyls relative to other neighboring groups in the protein matrix. [Pg.155]

Mossbauer spectroscopy The Mossbauer effect is resonance absorption of 7 radiation of a precisely defined energy, by specific nuclei. It is the basis of a form of spectroscopy used for studying coordinated metal ions. The principal application in bioinorganic chemistry is Fe. The source for the 7 rays is Co, and the frequency is shifted by the Doppler effect, moving it at defined velocities (in mm/s) relative to the sample. The parameters derived from the Mossbauer spectrum (isomer shift, quadrupole splitting, and the hyperfine coupling) provide information about the oxidation, spin and coordination state of the iron. [Pg.252]

Fig. 3 Signal of metronidazole anion radicals generated by hydrogenosomes of T. vaginalis in the presence of 45 mM metronidazole, pyruvate, CoA, and ferredoxin (activity of PFOR). Recorded by EPR spectroscopy at 25 °C with 20 mW of microwave power, a frequency of 9.64 GHz, and a modulation amplitude of 0.19 mT. The hyperfine coupling constants were n0no2 = 1 565 mT, Hfl4 = 0.542 mT, and - 0.229 mT... Fig. 3 Signal of metronidazole anion radicals generated by hydrogenosomes of T. vaginalis in the presence of 45 mM metronidazole, pyruvate, CoA, and ferredoxin (activity of PFOR). Recorded by EPR spectroscopy at 25 °C with 20 mW of microwave power, a frequency of 9.64 GHz, and a modulation amplitude of 0.19 mT. The hyperfine coupling constants were n0no2 = 1 565 mT, Hfl4 = 0.542 mT, and - 0.229 mT...

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