Laser pressure

The best characterized ion recombination systems are those involving irradiated rare gases. In the mid 1970 s rare gas-monohalide systems were extensively studied, due to their new-found application in u.v. exciplex lasers. Pulsed electron irradiation of these systems was the only major excitation method, as it allowed investigation under realistic laser pressure conditions of several atmospheres gas pressure. Typically these systems were investigated by monitoring of the time dependence of their characteristic peak fluorescence, as given in Table 12. 

Rotational temperatures T i < 1 K have been achieved with pulsed supersonic beams. A valve between the reservoir and nozzle opens for times Ar 0.1-1 ms with repetition frequencies / adapted to that of the pulsed lasers. Pressures po up to 100 bar are used, which demand only modest pumping speeds because of the small duty cycle Ar / 1. 

Lasers represent a special type of light source [16], [21], [60], [61]. They are used in trace analysis by fluorescence measurement or laser-induced fluorescence (LIF) (- Laser Analytical Spectroscopy) [62] - [64], in high-resolution spectroscopy, and in polarimetry for the detection of very small amounts of materials. Lasers can be of the gas. solid, or dye type [21]. In dye lasers, solutions of dyes are pumped optially by another laser or a flash lamp and then show induced emi.s-sion in some regions of their fluorescence bands. By tuning the resonator the decoupled dye laser line can be varied to a limited extent, so that what may be termed sequential laser spectrometers can be constructed [65]. In modern semiconductor lasers, pressure and temperature can also be used to detune the emission wavelength by 20-30nm [66], [67]. 

The efficiency of gas turbines is limited by the maximum allowable turbine inlet temperature (TIT). The TIT may be increased by cooling of the blades and vanes of the high pressure turbine. Cooling channels can be casted into the components or may be drilled afterwards. Non-conventional processes like EDM, ECD or Laser are used for drilling. Radiographic examination of the drilled components is part of the inspection procedure. Traditional X-Ray film technique has been used. The consumable costs, the waste disposal and the limited capacity of the two film units lead to the decision to investigate the alternative of Real-Time X-Ray. 

Recently, in situ studies of catalytic surface chemical reactions at high pressures have been undertaken [46, 47]. These studies employed sum frequency generation (SFG) and STM in order to probe the surfaces as the reactions are occurring under conditions similar to those employed for industrial catalysis (SFG is a laser-based teclmique that is described in section A 1.7.5.5 and section BT22). These studies have shown that the highly stable adsorbate sites that are probed under vacuum conditions are not necessarily tlie same sites that are active in high-pressure catalysis. Instead, less stable sites that are only occupied at high pressures are often responsible for catalysis. Because the active... 

For very fast reactions, as they are accessible to investigation by pico- and femtosecond laser spectroscopy, the separation of time scales into slow motion along the reaction path and fast relaxation of other degrees of freedom in most cases is no longer possible and it is necessary to consider dynamical models, which are not the topic of this section. But often the temperature, solvent or pressure dependence of reaction rate... 

Interest in AIN, GaN, InN and their alloys for device applications as blue light-emitting diodes and blue lasers has recently opened up new areas of high-pressure synthesis. Near atmospheric pressure, GaN and InN are nnstable with respect to decomposition to the elements far below the temperatures where they might melt. Thus, large boules of these materials typically used to make semiconductor devices caimot be grown from the... 

New metliods appear regularly. The principal challenges to the ingenuity of the spectroscopist are availability of appropriate radiation sources, absorption or distortion of the radiation by the windows and other components of the high-pressure cells, and small samples. Lasers and synchrotron radiation sources are especially valuable, and use of beryllium gaskets for diamond-anvil cells will open new applications. Impulse-stimulated Brillouin [75], coherent anti-Stokes Raman [76, 77], picosecond kinetics of shocked materials [78], visible circular and x-ray magnetic circular dicliroism [79, 80] and x-ray emission [72] are but a few recent spectroscopic developments in static and dynamic high-pressure research. 

Yoo C S, Akella J and Nicol M 1996 Chemistry at high pressures and temperatures in-situ synthesis and characterization of p-SijN by DAC x-ray/laser-heating studies Advanced Materials 96 ed M Akaishi et al (Tsukuba National Institute for Research in Inorganic Materials) p 175... 

Many optical studies have employed a quasi-static cell, through which the photolytic precursor of one of the reagents and the stable molecular reagent are slowly flowed. The reaction is then initiated by laser photolysis of the precursor, and the products are detected a short time after the photolysis event. To avoid collisional relaxation of the internal degrees of freedom of the product, the products must be detected in a shorter time when compared to the time between gas-kinetic collisions, that depends inversely upon the total pressure in the cell. In some cases, for example in case of the stable NO product from the H + NO2 reaction discussed in section B2.3.3.2. the products are not removed by collisions with the walls and may have long residence times in the apparatus. Study of such reactions are better carried out with pulsed introduction of the reagents into the cell or under crossed-beam conditions. 

With M = He, experimeuts were carried out between 255 K aud 273 K with a few millibar NO2 at total pressures between 300 mbar aud 200 bar. Temperature jumps on the order of 1 K were effected by pulsed irradiation (< 1 pS) with a CO2 laser at 9.2- 9.6pm aud with SiF or perfluorocyclobutaue as primary IR absorbers (< 1 mbar). Under these conditions, the dissociation of N2O4 occurs within the irradiated volume on a time scale of a few hundred microseconds. NO2 aud N2O4 were monitored simultaneously by recording the time-dependent UV absorption signal at 420 run aud 253 run, respectively. The recombination rate constant can be obtained from the effective first-order relaxation time, A derivation analogous to (equation (B2.5.9). equation (B2.5.10). equation (B2.5.11) and equation (B2.5.12)) yield... 

A recent example of laser flash-lamp photolysis is given by Hippier etal [ ], who investigated the temperature and pressure dependence of the thennal recombmation rate constant for the reaction... 

The experiments were perfonued in a static reaction cell in a large excess of N2 (2-200 bar). An UV laser pulse (193 mu, 20 ns) started the reaction by the photodissociation of N2O to fonu O atoms in the presence of NO. The reaction was monitored via the NO2 absorption at 405 mu using a Hg-Xe high-pressure arc lamp, together with direct time-dependent detection. With a 20-200-fold excess of NO, the fonuation of NO2 followed a pseudo-first-order rate law ... 

The microscopic understanding of tire chemical reactivity of surfaces is of fundamental interest in chemical physics and important for heterogeneous catalysis. Cluster science provides a new approach for tire study of tire microscopic mechanisms of surface chemical reactivity [48]. Surfaces of small clusters possess a very rich variation of chemisoriDtion sites and are ideal models for bulk surfaces. Chemical reactivity of many transition-metal clusters has been investigated [49]. Transition-metal clusters are produced using laser vaporization, and tire chemical reactivity studies are carried out typically in a flow tube reactor in which tire clusters interact witli a reactant gas at a given temperature and pressure for a fixed period of time. Reaction products are measured at various pressures or temperatures and reaction rates are derived. It has been found tliat tire reactivity of small transition-metal clusters witli simple molecules such as H2 and NH can vary dramatically witli cluster size and stmcture [48, 49, M and 52]. 

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. 

El = electron ionization Cl = chemical ionization ES = electrospray APCI = atmospheric-pressure chemical ionization MALDI = matrix-assisted laser desorption ionization PT = plasma torch (isotope ratios) TI = thermal (surface) ionization (isotope ratios). 

When mass spectrometry was first used as a routine analytical tool, El was the only commercial ion source. As needs have increased, more ionization methods have appeared. Many different types of ionization source have been described, and several of these have been produced commercially. The present situation is such that there is now only a limited range of ion sources. For vacuum ion sources, El is still widely used, frequently in conjunction with Cl. For atmospheric pressure ion sources, the most frequently used are ES, APCI, MALDI (lasers), and plasma torches. 

A laser beam is capable of putting so much energy into a substance in a very short space of time that the substance rapidly expands and volatilizes. The resulting explosive shock wave travels through the sample, subjecting it to high temperatures and pressures for short times. This process is also known as ablation. 

Until the advent of lasers the most intense monochromatic sources available were atomic emission sources from which an intense, discrete line in the visible or near-ultraviolet region was isolated by optical filtering if necessary. The most often used source of this kind was the mercury discharge lamp operating at the vapour pressure of mercury. Three of the most intense lines are at 253.7 nm (near-ultraviolet), 404.7 nm and 435.7 nm (both in the visible region). Although the line width is typically small the narrowest has a width of about 0.2 cm, which places a limit on the resolution which can be achieved. 

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