Absorption zero field microwave

In favorable cases, superconductivity is a sensitive and useful screen for desired crystals. Near zero field microwave absorption (95) can be used to examine very small samples of only a few micrograms. This technique has value in the search for new superconducting phases. In early attempts to identify the superconducting phase in the Pb-Sr-Y-Cu-O system, both superconducting and non-supercon-ducting crystals were obtained. Individual crystals were examined for superconductivity using near-zero field microwave absorption. Then X-ray diffraction was used to establish the structure and stoichiometry of the superconducting phase. 

The most precise measurements of the fine-structure parameters D and E have in fact been carried out using zero-field resonance. Figure 7.6 shows the three zero-field transitions in the Ti state of naphthalene molecules in a biphenyl crystal at T = 83 K. In these experiments, the absorption of the microwaves was detected as a function of their frequency [5]. The lines are inhomogeneously broadened and nevertheless only about 1 MHz wide. Owing to the small hnewidth of the zero-field resonances, the fine-structure constants can be determined with a high precision. This small inhomogeneous broadening is due to the hyperfine interaction with the nuclear spins of the protons (see e.g. [M2] and [M5]). For triplet states in zero field, the hyperfine structure vanishes to first order in perturbation theory, since the expectation value of the electronic spins vanishes in all three zero-field components (cf Sect. 7.2). The hyperfine structure of the zero-field resonances is therefore a second-order effect [5]. 

An example of a quantitatively-analysed experimental result for these constants is shown in Fig. 7.29 in mixed crystals of naphthalene-dg 0.1% quinoxaline, the ESR transition T. To for the field direction Bo Xquinoxaiine and at a temperature T = 1.8 K is an absorption signal in the stationary state (Fig. 7.29a), while the transition I To) T-) in the stationary state exhibits stimulated emission of microwaves (Fig. 7.29b). After the end of the UV excitation at t = 0, the absorption line temporarily becomes an emission tine and vice versa. The interpretation of these results is simple (Fig. 7.29d) due to the negligible spin-lattice relaxation at T= 1.8 K, the three Zeeman components decay after the end of the U V excitation independently of one another, each with its own lifetime tj = into the So ground state. Since the difference of the populations of the three states is directly proportional to the intensity of the ESR signals, their time dependence can be used to determine the individual lifetimes of the Zeeman components involved. In the case of the particular orientation Boll, the state is To) = IT ), and one obtains directly from the measurements, e.g. the decay constant feo = kx and thus the lifetime of the zero-field constant Tx) of quinoxaline. 

In the method known as ADMR, the microwave transitions between the individual triplet sublevels are detected by means of a change in the optical absorption of the singlet ground state. This is based on a redistribution of the population between the three different triplet substates (zero-field states without, or Zeeman states with an external magnetic field) with different decay constants ( spin-polarisation ) if for example the spin population is pumped by microwave irradiation from a shortlived sublevel to a long-Hved one, then the overall triplet population is increased, while the population of the singlet ground state decreases. 

At low microwave fields transitions involving only a few photons are observed, at high static fields, near the field of the avoided crossing. As the microwave field is increased more transitions are observed, at progressively lower static fields, until at the highest microwave fields the sequence of resonant transitions extends to zero static field. As shown by the scale at the top of Fig. 10.9 the 18s —> (16,3) transition nearest zero static field corresponds to the absorption of 28 photons. 

Microwave-based meters have also been used to monitor water content in emulsions (39). Microwave techniques can be used in two ways Either the attenuation of the microwave radiation due to absorption by the water phase is measured, or capacitance or resonance changes in a microwave cavity are noted. The capacitance-change method is much more sensitive, although both, like the gamma-ray absorption method, are limited in that solids content must be constant or zero in order to accurately interpret the information obtained. Both of these techniques are applicable to field situations and on-line monitoring. 

The synthesis of macroscopic amounts of C o and C70 (fullerenes) has stimuiated a variety of studies on their chemical and physical properties. We recently demonstrated that C o and C70 become conductive when doped with alkali metals. Here we describe iow-temperature studies of potassium-doped both as films and bulk samples, and demonstrate that this material becomes superconducting, Superconductivity is demonstrated by microwave, resistivity and Melssner-effect measurements. Both polycrystalline powders and thin-flim samples were studied. A thin film showed a resistance transition with an onset temperature of 16 K and essentially zero resistance near 5 K. Bulk samples showed a well-defined Meissner effect and magnetic-field-dependent microwave absorption beginning at 18 K. The onset of superconductivity at 18 K is the highest yet observed for a molecular superconductor. 

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