Atomizers laser spectroscopy

In atomic laser spectroscopy, the laser radiation, which is tuned to a strong dipole transition of the atoms under investigation, penetrates the volume of species evaporated from the sample. The presence of analyte atoms can be measmed by means of the specific interaction between atoms and laser photons, such as by absorption techniques (laser atomic absorption spectrometry, LAAS), by fluorescence detection (laser-induced fluorescence spectroscopy, LIFS), or by means of ionization products (electrons or ions) of the selectively excited analyte atoms after an appropriate ionization process (Figures lA and IB). Ionization can be achieved in different ways (1) by interaction with an additional photon of the exciting laser or of a second laser (resonance ionization spectroscopy, RIS, or resonance ionization mass spectrometry, RIMS, respectively, if combined with a mass detection system) (2) by an electric field applied to the atomization volume (field-ionization laser spectroscopy, FILS) or (3) by collisional ionization by surrounding atoms (laser-enhanced ionization spectroscopy, LEIS). 

NEW THEORETICAL TOOLS FOR SINGLE ATOM LASER SPECTROSCOPY... 

Doppler-Broadened Transition. Narrow Resonances of Two-Photon Transitions Willioul Doppler Broadening.—Nonlinear Resonances on Coupled Doppler-Broadened Transitions. Narrow Nonlinear Resonances in Spectroscopy. Nonlinear Atomic Laser Spectroscopy. Nonlinear Molecular Laser Spectroscopy. - Nonlinear Narrow Resonances in Quantum Electronics. Narrow Nonlinear Resonances in Experimental Physics. 

The spectroscopy of ion lasers is generally less well understood than that of neutral atom lasers because of the lack of detailed knowledge of ion energy-level schemes. Indeed, ion lasers were first produced accidentally and attempts to assign the transitions came later. 

Laser spectroscopy is such a wide subject, with many ingenious experiments using one or two CW or pulsed lasers to study atomic or molecular stmcture or dynamics, that it is difficult to do justice to it at the level at which Modern Spectroscopy is aimed. In this edition 1 have expanded the section on supersonic jet spectroscopy, which is an extremely important and wide-ranging field. 

In dimers composed of equal molecules the dimer components can replace each other through tunneling. This effect has been discovered by Dyke et al. [1972] as interconversion splitting of rotational levels of (HF)2 in molecular beam electric resonance spectra. This dimer has been studied in many papers by microwave and far infrared tunable difference-frequency laser spectroscopy (see review papers by Truhlar [1990] and by Quack and Suhm [1991]). The dimer consists of two inequivalent HE molecules, the H atom of one of them participating in the hydrogen bond between the fluorine atoms (fig. 60). PES is a function of six variables indicated in this figure. 

Figure 4.21 Evidence for the hot atom concept from ionisation laser spectroscopy.

The emerging analytical technique of laser-induced breakdown spectroscopy (LIBS) is a simple atomic emission spectroscopy technique that has the potential for real-time man-portable chemical analysis in the field. Because LIBS is simultaneously sensitive to all elements, a single laser shot can be used to record the broadband emission spectra, which provides a chemical fingerprint of a material. 

Hinkl, E. D., K. W. Nill, and F. A. Blum. Infrared spectroscopy with tunable lasers, pp. 125-1%. In H. Walther, Ed. Laser Spectroscopy of Atoms and Molecules. New York Springer-Verlag, 1976. 

Atomic absorption signal from 60 gaseous rubidium atoms observed by laser wave mixing. A 10-microliter (10 x 10 6 L) sample containing 1 attogiam (1 x 10-18 g) of Rb was injected into a graphite furnace to create the atomic vapor. We will study atomic absorption spectroscopy in Chapter 21. [R K. Mickadelt,... 

Since the mid-1960s, a variety of analytical chemistry techniques have been used to characterize obsidian sources and artifacts for provenance research (4, 32-36). The most common of these methods include optical emission spectroscopy (OES), atomic absorption spectroscopy (AAS), particle-induced X-ray emission spectroscopy (PIXE), inductively coupled plasma-mass spectrometry (ICP-MS), laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), X-ray fluorescence spectroscopy (XRF), and neutron activation analysis (NAA). When selecting a method of analysis for obsidian, one must consider accuracy, precision, cost, promptness of results, existence of comparative data, and availability. Most of the above-mentioned techniques are capable of determining a number of elements, but some of the methods are more labor-intensive, more destructive, and less precise than others. The two methods with the longest and most successful histoty of success for obsidian provenance research are XRF and NAA. 

Hyperfine structure measurements using on-line atomic-beam techniques are of great importance in the systematic study of spins and moments of nuclei far from beta-stability. We will discuss the atomic-beam magnetic resonance (ABMR) method, and laser spectroscopy methods based on crossed-beam geometry with a collimated thermal atomic-beam and collinear geometry with a fast atomic-beam. Selected results from the extensive measurements at the ISOLDE facility at CERN will be presented. 

As mentioned above, the radon and radium sequences have been investigated by collinear fast-beam laser spectroscopy, whereas in francium all three atomic-beam methods, ABMR, atomic-beam laser spectroscopy and collinear laser spectroscopy, have contributed. 

Several groups at ISOLDE are planning further improvements of their techniques. For each element the most appropriate experimental scheme has to be found. Today, collinear laser spectroscopy is the most general high-resolution and sensitive method for optical spectroscopy on radioactive beams delivered by on-line mass separators. Its sensitivity ranges from 10 - 10 atoms/s depending on the strength and multiplicity of the optical transitions. 

The rest of the apparatus is the same as when operated at the Proton Synchrotron. First tested on cesium [ HUB 78 ], [ THI 81 ] the apparatus was used to uncover the resonance lines of francium for which no optical transition had ever been observed. The CERN on line mass separator, Isolde, makes available a source of more than 10 atoms/sec of chemically and isotopically pure 213 Fr isotope. Such an amount is more than needed for a laser atomic beam spectroscopy. The first step is obviously to locate the resonance line at low resolution, using a broad band laser excitation. In a second step, once the line is located, a high resolution study is undertaken, [ LIB 80] and [ BEN 84]. The observed signal is displayed (fig 3a) at low resolution and(3 b)at high resolution. 

The schematic view of the Mainz apparatus for collinear laser spectroscopy, installed at Isolde is given in fig 4. The 60 keV ion beam is set collinear with the laser beam, then accelerated (or decelerated) and finally neutralized in charge exchange cell. By Doppler tuning the atomic absorption is set resonnant with the stabilized laser frequency, and the fluorescence emitted is detected. 

Because of the velocity bunching effect due to initial acceleration the ion beam is nearly monokinetic, and the neutralisation does not effect the velocity distribution The details of the method can be found in [ KAUF 78 ], [ NUE 78] By neutralisation in an alkali vapour, the atomic metastable states are preferentially populated since their energies match the ionisation potential of the corresponding alkali atom Therefore this technic is ideally suited for laser spectroscopy of rare gas, and is recently successfully used to study the heaviest one, radon Fig. 

AMS = accelerated mass spectroscopy EDTA = ethylene diamine tetra acetic acid GFAAS = graphite furnace atomic absorption spectrometry ICP-AES = inductively coupled plasma - atomic emission spectroscopy NAA = neutron activation analysis ETAAS = electrothermal atomic absorption spectrometry SEC/ICP-MS = size-exclusion chromatography/ICP-AES/mass spectrometry HLPC/ICP-AES = high-performance liquid chromatography/ICP-AES LAMMA = laser ablation microprobe mass analysis NA = not applicable ppq = parts per quadrillion... 

The rare earth elements are different from other elements because the optical transitions between levels of the fn configuration are inherently very sharp-lined and have well-resolved structure characteristic of the local crystal fields around the ion. In minerals, this characteristic provides an excellent probe of the local structure at the atomic level. Examples will be shown from our work of how site selective laser spectroscopy can be used to determine the thermal history of a sample, the point defect equilibria that are important, the presence of coupled ion substitution, the determination of multiple phases, and stoichiometry of the phase. The paper will also emphasize the fact that the usefulness and the interpretation of the rare earth luminescence is complicated by the presence of quenching and disorder in mineral samples. One in fact needs to know a great deal about a sample before the wealth of information contained in the site selective luminescence spectrum can be understood. 

Our research group at the University of Wisconsin has developed a new approach to the study of minerals that can provide great detail at the atomic level. Our program is founded on the idea that site selective laser spectroscopy can be used to simplify the spectra of complex materials. Recent reviews of our work are published in reference 1. The methods can be used to ... 

Decomps, B., Dumont, M. and Duclqy, M. (1976). Linear and nonlinear phenomena in laser optical pumping. In Laser Spectroscopy of Atoms and Molecules. Topics in Applied Physics, vol. 2, ed. H. Walther, pp. 283-347 (Springer-Verlag, Berlin, Heidelberg, New York). 

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