Microwave sensitivities

The microwave conductivity is proportional to the number of free electronic charge carriers multiplied by their respective mobilities (the contribution of ions and dipoles can be neglected in a first approximation.). The microwave sensitivity constant S must be obtained by calibration. The potential-dependent photoinduced microwave conductivity (PMC) of a semiconductor resulting from illumination has been calculated analytically as a function of the interfacial charge-transfer and surface recombination rates (Schlichthorl and Tributsch, 1992). The starting point is the general set of equations of the form... 

A microwave pulse from a tunable oscillator is injected into the cavity by an anteima, and creates a coherent superposition of rotational states. In the absence of collisions, this superposition emits a free-mduction decay signal, which is detected with an anteima-coupled microwave mixer similar to those used in molecular astrophysics. The data are collected in the time domain and Fourier transfomied to yield the spectrum whose bandwidth is detemimed by the quality factor of the cavity. Hence, such instruments are called Fourier transfomi microwave (FTMW) spectrometers (or Flygare-Balle spectrometers, after the inventors). FTMW instruments are extraordinarily sensitive, and can be used to examine a wide range of stable molecules as well as highly transient or reactive species such as hydrogen-bonded or refractory clusters [29, 30]. 

As described above, classical infrared spectroscopy using grating spectrometers and gas cells provided some valuable infonnation in the early days of cluster spectroscopy, but is of limited scope. However, tire advent of tunable infrared lasers in tire 1980s opened up tire field and made rotationally resolved infrared spectra accessible for a wide range of species. As for microwave spectroscopy, tunable infrared laser spectroscopy has been applied botli in gas cells and in molecular beams. In a gas cell, tire increased sensitivity of laser spectroscopy makes it possible to work at much lower pressures, so tliat strong monomer absorjDtions are less troublesome. 

It is important to realize that electronic spectroscopy provides the fifth method, for heteronuclear diatomic molecules, of obtaining the intemuclear distance in the ground electronic state. The other four arise through the techniques of rotational spectroscopy (microwave, millimetre wave or far-infrared, and Raman) and vibration-rotation spectroscopy (infrared and Raman). In homonuclear diatomics, only the Raman techniques may be used. However, if the molecule is short-lived, as is the case, for example, with CuH and C2, electronic spectroscopy, because of its high sensitivity, is often the only means of determining the ground state intemuclear distance. 

The longest wavelengths of the electromagnetic spectmm are sensitive probes of molecular rotation and hyperfine stmcture. An important appHcation is radio astronomy (23—26), which uses both radio and microwaves for chemical analysis on galactic and extragalactic scales. Herein the terrestrial uses of microwave spectroscopy are emphasized (27—29). 

Microwave spectroscopy is used for studyiag free radicals and ia gas analysis (30). Much laboratory work has been devoted to molecules of astrophysical iaterest (31). The technique is highly sensitive 10 mole may suffice for a spectmm. At microwave resolution, frequencies are so specific that a single line can unambiguously identify a component of a gas mixture. Tabulations of microwave transitions are available (32,33). Remote atmospheric sensing (34) is illustrated by the analysis of trace CIO, O, HO2, HCN, and N2O at the part per trillion level ia the stratosphere, usiag a ground-based millimeter-wave superheterodyne receiver at 260—280 GH2 (35). 

The intrinsic drawback of LIBS is a short duration (less than a few hundreds microseconds) and strongly non-stationary conditions of a laser plume. Much higher sensitivity has been realized by transport of the ablated material into secondary atomic reservoirs such as a microwave-induced plasma (MIP) or an inductively coupled plasma (ICP). Owing to the much longer residence time of ablated atoms and ions in a stationary MIP (typically several ms compared with at most a hundred microseconds in a laser plume) and because of additional excitation of the radiating upper levels in the low pressure plasma, the line intensities of atoms and ions are greatly enhanced. Because of these factors the DLs of LA-MIP have been improved by one to two orders of magnitude compared with LIBS. 

Microwave measurements are typically performed at frequencies between 8 and 40 Gc/s. The sensitivity with which photogenerated charge carriers can be detected in materials by microwave conductivity measurements depends on the conductivity of the materials, but it can be very high. It has been estimated that 109-1010 electronic charge carriers per cubic centimeter can be detected. Infrared radiation can, of course, also be used to detect and measure free electronic charge carriers. The sensitivity for such measurements, however, is several orders of magnitude less and has been estimated to be around 1015 electronic charge carriers per cubic centimeter.1 Microwave techniques, therefore, promise much more sensitive access to electrochemical mechanisms. 

As with alternating electrical currents, phase-sensitive measurements are also possible with microwave radiation. The easiest method consists of measuring phase-shifted microwave signals via a lock-in technique by modulating the electrode potential. Such a technique, which measures the phase shift between the potential and the microwave signal, will give specific (e.g., kinetic) information on the system (see later discussion). However, it should not be taken as the equivalent of impedance measurements with microwaves. As in electrochemical impedance measurements,... 

Figure 9. (a) Electrode and representative circuit for phase-sensitive electrochemical measurements (impedance measurements) compared with (b) setup for phase-sensitive microwave (impedance) measurements. 

Electrochemical impedance spectroscopy leads to information on surface states and representative circuits of electrode/electrolyte interfaces. Here, the measurement technique involves potential modulation and the detection of phase shifts with respect to the generated current. The driving force in a microwave measurement is the microwave power, which is proportional to E2 (E = electrical microwave field). Therefore, for a microwave impedance measurement, the microwave power P has to be modulated to observe a phase shift with respect to the flux, the transmitted or reflected microwave power APIP. Phase-sensitive microwave conductivity (impedance) measurements, again provided that a reliable theory is available for combining them with an electrochemical impedance measurement, should lead to information on the kinetics of surface states and defects and the polarizability of surface states, and may lead to more reliable information on real representative circuits of electrodes. We suspect that representative electrical circuits for electrode/electrolyte interfaces may become directly determinable by combining phase-sensitive electrical and microwave conductivity measurements. However, up to now, in this early stage of development of microwave electrochemistry, only comparatively simple measurements can be evaluated. 

Other ways to determine the sensitivity factor S are possible, for example, by comparing microwave reflectance and admittance responses in a potential region with ideal junction behavior.31... 

At present, the microwave electrochemical technique is still in its infancy and only exploits a portion of the experimental research possibilities that are provided by microwave technology. Much experience still has to be gained with the improvement of experimental cells for microwave studies and in the adjustment of the parameters that determine the sensitivity and reliability of microwave measurements. Many research possibilities are still unexplored, especially in the field of transient PMC measurements at semiconductor electrodes and in the application of phase-sensitive microwave conductivity measurements, which may be successfully combined with electrochemical impedance measurements for a more detailed exploration of surface states and representative electrical circuits of semiconductor liquid junctions. 

Cyclic ureas can be obtained by reaction of simple urea with 1,2-diamino derivatives in DMF in the presence of ZnO and under microwave irradiation (Scheme 53). In this unusual condensation, two molecules of ammonia are eliminated. The reaction is very sensitive to the presence of ZnO. Without this catalyst, a yield of 20% is reported together with the formation of several by-products. The reaction was also carried out under reduced pressure... 

For the synthesis of quinolines and isoquinolines the classical approaches are the Skraup and the Bischler-Napieralski reactions. The reaction of substituted anilines with different carbonyl compounds in acid medium has been reported to be accelerated under microwave irradiation to give differently substituted quinolines and dihydro quinolines [137]. Although the yields are much better and the conditions are milder than under conventional heating, the acidity of the medium may prevent the preparation of acid-sensitive compounds. Thus, alternative approaches have been investigated. Substituted anilines and alkyl vinyl ketones reacted under microwave irradiation on the surface of sihca gel doped with InCU without solvent [137] to furnish good yields of quinohnes 213 (Scheme 77). 

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