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Echo-detected electron spin resonance

Electron Spin Resonance Spectroscopy. Several ESR studies have been reported for adsorption systems [85-90]. ESR signals are strong enough to allow the detection of quite small amounts of unpaired electrons, and the shape of the signal can, in the case of adsorbed transition metal ions, give an indication of the geometry of the adsorption site. Ref. 91 provides a contemporary example of the use of ESR and of electron spin echo modulation (ESEM) to locate the environment of Cu(II) relative to in a microporous aluminophosphate molecular sieve. [Pg.586]

Double-resonance spectroscopy involves the use of two different sources of radiation. In the context of EPR, these usually are a microwave and a radiowave or (less common) a microwave and another microwave. The two combinations were originally called ENDOR (electron nuclear double resonance) and ELDOR (electron electron double resonance), but the development of many variations on this theme has led to a wide spectrum of derived techniques and associated acronyms, such as ESEEM (electron spin echo envelope modulation), which is a pulsed variant of ENDOR, or DEER (double electron electron spin resonance), which is a pulsed variant of ELDOR. The basic principle involves the saturation (partially or wholly) of an EPR absorption and the subsequent transfer of spin energy to a different absorption by means of the second radiation, leading to the detection of the difference signal. The requirement of saturability implies operation at close to liquid helium, or even lower, temperatures, which, combined with long experimentation times, produces a... [Pg.226]

The intent of this chapter is not to survey noninvasive surface spectroscopy but to illustrate briefly how it is applied to resolve the Stummian issue of whether inner-sphere surface complexes form. For this purpose, the application of electron spin resonance (ESR), electron nuclear double resonance (ENDOR), and electron spin echo envelope modulation (ESEEM) spectroscopies to elucidate metal cation speciation and the use of extended X-ray absorption fine structure (EXAFS) spectroscopy to detect surface anion species will be described. Emphasis will be on the interpretation of spectra. Sample preparation and instrumentation details were reviewed in recent volumes edited by Hawthorne (55) and Perry (27). Because the constant capacitance model was developed in the context of adsorption by hydrous oxides, these... [Pg.45]

Since electron spin resonance is an excellent analytical method for paramagnetic species and free radicals, it can be used to obtain a variety of kinetic and thermodynamic data. In this respect it is used in the same way as any other spectroscopic technique. Kinetic data can be obtained by studying radical intensity versus time. By using time-domain electron magnetic resonance techniques such as electron spin-echo spectroscopy, one can detect transient species with lifetimes as short as 100 nsec. [Pg.132]

Electron-nuclear double resonance (ENDOR) spectroscopy A magnetic resonance spectroscopic technique for the determination of hyperfine interactions between electrons and nuclear spins. There are two principal techniques. In continuous-wave ENDOR the intensity of an electron paramagnetic resonance signal, partially saturated with microwave power, is measured as radio frequency is applied. In pulsed ENDOR the radio frequency is applied as pulses and the EPR signal is detected as a spin-echo. In each case an enhancement of the EPR signal is observed when the radiofrequency is in resonance with the coupled nuclei. [Pg.250]

Valuable spectroscopic studies on the dithiolene chelated to Mo in various enzymes have been enhanced by the knowledge of the structure from X-ray diffraction. Plagued by interference of prosthetic groups—heme, flavin, iron-sulfur clusters—the majority of information has been gleaned from the DMSO reductase system. The spectroscopic tools of X-ray absorption spectroscopy (XAS), electronic ultraviolet/visible (UV/vis) spectroscopy, resonance Raman (RR), MCD, and various electron paramagnetic resonance techniques [EPR, electron spin echo envelope modulation (ESEEM), and electron nuclear double resonance (ENDOR)] have been particularly effective probes of the metal site. Of these, only MCD and RR have detected features attributable to the dithiolene unit. Selected results from a variety of studies are presented below, chosen because their focus is the Mo-dithiolene unit and organized according to method rather than to enzyme or type of active site. [Pg.515]

In the last few years, pulsed EPR or electron spin echo (ESE) and reaction yield detected magnetic resonance (RYDMAR) techniques have been added to the arsenal of EPR techniques applied in photosynthesis. ESE combines high temporal resolution (currently 100 ns) with sensitivity to broad EPR signals, and it allows rapid and accurate determination of the spin-lattice and spin-spin relaxation times. [Pg.117]

Complex 146 (entry 0-3 of Table 3) forms a free radical in THF solution and the electron paramagnetic resonance (EPR) spectrum shows a weak triplet signal with hyperflne splitting by coupling with the P ligands. The triplet disappears when Ag(0) precipitates. The presence of covalent radicals [Ag—CH(R)OH]"+, R = H, Me, in Ag(l)-containing molecular sieves loaded with MeOH or EtOH was detected by EPR and electron spin echo envelope modulation spectroscopies. ... [Pg.187]

The pulse EPR methods discussed here for measuring nuclear transition frequencies can be classified into two categories. The first involves using electron nuclear double resonance (ENDOR) techniques where flie signal arises from the excitation of EPR and NMR transitions by microwave (m.w.) and radiofrequency (r.f) irradiation, respectively. In the second class of experiments, based on flic electron spin echo envelope modulation (ESEEM) effect, flic nuclear transition frequencies are indirectly measured by the creation and detection of electron or nuclear coherences using only m.w. pulses. No r.f irradiation is required. ENDOR and ESEEM spectra often give complementary information. ENDOR experiments are especially suited for measuring nuclear frequencies above approximately 5 MHz, and are often most sensitive when the hyperfine interaction in not very anisotropic. Conversely, anisotropic interactions are required for an ESEEM effect, and the technique can easily measure low nuclear frequencies. [Pg.14]

In Davies ENDOR the first selective m.w. n pulse inverts the polarization of a particular EPR transition (Fig. 15a). During the miKing period a selective r.f. a pulse is applied. If the r.f pulse is resonant with one of the nuclear frequencies (Fig. 15b), the polarization of this transition is inverted, which also alters the polarization of the electron spin echo observer transition (1,3) detected via a primary echo, a/2 - T - % - X - echo. The ENDOR spectrum is thus recorded by monitoring the primary echo intensity as the r.f frequency is incremented stepwise over the desired frequency range. [Pg.41]

A large variety of hyperfine spectroscopy methods exist that allow the detection of hyperfine and nuclear quadrupole interactions electron spin-echo envelope modulation (ESEEM), ENDOR, and ELDOR-detected NMR (electron-electron doubleresonance detected nuclear magnetic resonance) [13]. Although there are cases in which ESEEM and ENDOR perform equally well, ESEEM-like methods tend to be... [Pg.6]


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Echo Detectability

Electron detection

Electron spin echo

Electron spin-echo resonance

Resonance Detection

Resonant detection

Spin detection

Spin echo detection

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