Laser resonance ionization 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). 

In other articles in this section, a method of analysis is described called Secondary Ion Mass Spectrometry (SIMS), in which material is sputtered from a surface using an ion beam and the minor components that are ejected as positive or negative ions are analyzed by a mass spectrometer. Over the past few years, methods that post-ion-ize the major neutral components ejected from surfaces under ion-beam or laser bombardment have been introduced because of the improved quantitative aspects obtainable by analyzing the major ejected channel. These techniques include SALI, Sputter-Initiated Resonance Ionization Spectroscopy (SIRIS), and Sputtered Neutral Mass Spectrometry (SNMS) or electron-gas post-ionization. Post-ionization techniques for surface analysis have received widespread interest because of their increased sensitivity, compared to more traditional surface analysis techniques, such as X-Ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES), and their more reliable quantitation, compared to SIMS. 

Laser enhanced ionization spectroscopy and resonance ionization spectroscopy... 

Resonance ionization spectroscopy is a photophysical process in which one electron can be removed from each of the atoms of a selected type. Since the saturated RIS process can be carried out with a pulsed laser beam, the method has both time and space resolution along with excellent (spectroscopic) selectivity. In a recent article [2] we showed, for example, that all of the elements except helium, neon, argon, and fluorine can be detected with the RIS technique. However, with commercial lasers, improved in the last year, argon and fluorine can be added to the RIS periodic table (see figure 2). 

Resonant and non-resonant laser post-ionization of sputtered uranium atoms using SIRIS (sputtered initited resonance ionization spectroscopy) and SNMS (secondary neutral mass spectrometry) in one instrument for the characterization of sub-pm sized single microparticles was suggested by Erdmann et al.94 Resonant ionization mass spectrometry allows a selective and sensitive isotope analysis without isobaric interferences as demonstrated for the ultratrace analysis of plutonium from bulk samples.94 Unfortunately, no instrumental equipment combining both techniques is commercially available. 

Resonance ionization spectroscopy (RIS) with pulsed tunable lasers offers new possibilities for constructing pulsed, highly selective ion sources with high efficiencies. Fig. 4 shows the principle of RIS and the planned set up. The efficiency of the ion source is determined mainly by the ratio of the repetition rate... 

Fig. 4 Right Principle of resonance ionization spectroscopy. Three tunable pulsed Dye lasers are used to stepwize excite and ionize the atom. The effective cross-sections are indicated for the different transitions in cm2. Left Layout of a laser ion source for on-line mass separators.

Graphite furnace AAS Atomic fluorescence spectroscopy Inductively-coupled-plasma optical-emission spectroscopy Glow-discharge optical-emission spectroscopy Laser-excited resonance ionization spectroscopy Laser-excited atomic-fluorescence spectroscopy Laser-induced-breakdown spectroscopy Laser-induced photocoustic spectroscopy Resonance-ionization spectroscopy... 

Hi) Methods based on mass spectrometry Spark-source mass spectrometry Glow-discharge mass spectrometry Inductively coupled-plasma mass spectrometry Electro-thermal vaporization-lCP-MS Thermal-ionization mass spectrometry Accelerator mass spectrometry Secondary-ion mass spectrometry Secondary neutral mass spectrometry Laser mass spectrometry Resonance-ionization mass spectrometry Sputter-initiated resonance-ionization spectroscopy Laser-ablation resonance-ionization spectroscopy... 

Laser excited resonance ionization spectroscopy (LERIS)... 

Laser-Ablation Resonance-Ionization Spectroscopy LARIS... 

LEIS laser-enhanced ionization spectroscopy FILS field ionization laser spectroscopy RIS resonance ionization spectroscopy RIMS resonance ionization mass spectrometry... 

The ionization potential of an element is one of its fundamental properties. It is known that the first ionization potential of heavy elements depends on relativistic effects. The Mainz group, in Germany, systematically determined the first ionization potential of the actinide elements from Ac through Es using laser spectroscopy as shown in Table 18.12 (Becke et al. 2002). O Figure 18.24 shows the comparison of ionization potentials between lanthanide and actinide atoms (Moore 1971 Becke et al. 2002). The atomic level structure of Fm (2.7 x 10 ° atoms) with a half-life of 20.1 h was studied for the first time by the method of resonance ionization spectroscopy. Two atomic levels were identified at wave numbers (25,099.8 0.2) cm and (25,111.8 0.2) cm (Sewtz et al. 2003). 

Once the charged particles, ions and electrons, are formed they can be extracted out of the laser beam-molecule interaction volume and monitored using a charge-sensitive detector. The general principle to implement (resonant) ionization spectroscopy is shown in Figure 9.1. 

Some less common acronyms for laser SNMS are also used, such as sputter-initiated resonance ionization spectroscopy (SIRIS) [287] and surface analysis by laser ionization (SALI) [288]. 

Parks, J.E. (1990) Surface analysis using resonance ionization spectroscopy. In Lasers and Mass Spectrometry, edited by Lubman, D.M. New York Oxford University Press, pp. 37-64. 

Resonance ionization spectroscopy (RIS) is based on resonance multistep excitation of high-lying levels of free analyte atoms and their subsequent ionization. Ionization may be caused by the photons of the final laser step (photoioniza-... 

Figure lA. Resonance ionization spectroscopy is performed by monitoring molecular ions while tuning the laser wavelength. If the energy of one photon is in resonance with a neutral electronic excited state a second photon is able to be absorbed, giving rise to an ion current peak. Thus, the neutral UV-absorption spectrum is transferred to the ion current which can be recorded mass selectively (in opposition to the absorption). Thus UV spectroscopy and mass spectroscopy are combined as a two-dimensional technique. 

Figure ID. If a tunable laser is used for secondary excitation of molecular ions, resonance dissociation spectroscopy of molecular cations may be performed. Here excited cationic levels are subject to laser spectroscopy. They serve as intermediate states for the process of resonance enhanced multiphoton dissociation. This is quite similar to resonance ionization spectroscopy of neutrals. The difference is that a dissociation instead of an ionization continuum is finally reached by multiphoton excitation. The advantage of this technique is that it is independent of high ion numbers (as necessary for absorption spectroscopy), fluorescence [necessary for laser-induced fluorescence (LIF)] or predissociation and therefore is fairly general. In addition, mass selectivity is intrinsic and one may benefit from state selective ion formation if resonance multiphoton ionization is used as an ion source.

Kim NJ, Jeong G, Kim YS, Sung J, Kim SK, Park YD (2000) Resonant two-photon ionization and laser induced fluorescence spectroscopy of jet-cooled adenine. J Chem Phys 113 10051... 

On-line conpling of capillary electromigration techniques with nuclear magnetic resonance spectroscopy [5] and matrix-assisted laser desorption/ionization (MALDl) time-of-flight (TOF) mass spectrometry [6] has also been reported. 

G. Gerber By applying two-photon ionization spectroscopy with tunable femtosecond laser pulses we recorded the absorption through intermediate resonances in cluster sizes Na with n = 3,. 21. The fragmentation channels and decay pattern vary not only for different cluster sizes but also for different resonances corresponding to a particular size n. This variation of r and the fragmentation channels cannot be explained by collective type processes (jellium model with surface plasmon excitation) but rather require molecular structure type calculations and considerations. 

Abbreviations AOD, Acousto-optical deflection BCB, bisbenzyocyclobutadiene CCD, indirect contact conductivity detection CL, chemiluminescence ECD, electron capture detector FCS, fluorescence correlation spectroscopy FRET, fluorescence resonance energy transfer ICCD, integrated contact conductivity detection GMR, giant magnetoresistive LED-CFD, light emitting diode confocal fluorescence detector LIF, laser-induced fluorescence LOD, limit of detection MALDI, matrix-assisted laser desorption ionization PDMS, poly(dimethylsiloxane) PMMA, poly(methylmetha-crylate) SPR, surface plasmon resonance SVD, sinusoidal voltammetric detection TLS, thermal lens spectroscopy. 

MALDI MCM-41 MCR MD ME MEM MI MPM MRI MS MVA Matrix-assisted Laser Desorption/Ionization Mobile Crystalline Material-41 Multivariate Curve Resolution Molecular Dynamics Matrix-enhanced Magnetic Force Micrscopy Multivariate Image Multiphoton Microscopy Magnetic Resonance Imaging Mass Spectroscopy Multivariate Analysis... 

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