Resonant laser ionization

Resonance ionization mass spectrometry as a combination of resonance laser ionization with mass spectrometry can be performed on gas atoms only. Therefore, in RIMS of solid samples, before resonance ionization, a neutral gas has to be produced using several methods known from solid state mass spectrometry. During the evaporation of solid material, e.g., by laser evaporation, thermal evaporation or by sputtering with a primary ion beam, the formation of ions should to be avoided. In RIMS, mostly the thermal evaporation of sample from a heated W or Re filament is applied. 

Whereas in LIMS only one laser with defined wavelength (e.g., Nd YAG - 1064 nm) is used for direct vaporization and ionization of solid samples in laser plasma, in resonance ionization mass spectrometry (RIMS) one or more lasers are tuned precisely to the wavelength required for the excited states and ionization of evaporated atoms in order to get a highly selective ionization of the analyte. The basic principles of resonant ionization were first described by Hurst and coworkers at Oak Ridge National Laboratory as well as by Letokhov et in Russia. The technology 

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Resonant (R-) laser-SNMS [3.107-3.112] has almost all the advantages of SIMS, e-SNMS, and NR-laser-SNMS, with the additional advantage of using a resonance laser ionization process which selectively and efficiently ionizes the desired elemental species over a relatively large volume (Eig. 3.40 C). Eor over 80% of the elements in the periodic table, R-laser-SNMS has almost unity ionization efficiency over a large volume, so the overall efficiency is greater than that of NR-laser-SNMS. Quantification is also simpler because the unsaturated volume (where ionization is incom-... 

Different mass spectrometric techniques can be classified according to the evaporation and ionization methods applied. Evaporation of solid samples can be performed, for example, by thermal (e.g., on a hot tantalum filament or in a heated graphite furnace) or laser-induced evaporation, and by electron or ion bombardment. Electron ionizaton (El), ionization during the sputtering process with a primary ion beam, resonant or non-resonant laser ionization or thermal surface ionization... 

The most common LA-ICP/MS work to date is with flash-lamp pumped Nd YAG lasers that produce a light pulse of 3-10 nanoseconds in width and are relatively inexpensive. Shorter pulse width lasers (picosecond to femtosecond) are widely available but more expensive. A wavelength other than IR or UV is used only for resonant laser ionization or ablation. In this case, the goal is to excite or ionize a specific element preferentially, and the laser wavelength is chosen to correspond to a particular transition of an element, as discussed in Section 17.7.4. 

Wendt, K., Trautmann, N., and Bushaw, B. A. 2000. Resonant laser ionization mass spectrometry An alternative to AMS Nucl Instrum Meth B 172, 162-169. 

In VoL 2 of this handbook, the origin of elements has been discussed in detail. Therefore, the present authors will exclude that part, except for some comments on the importance of particular radionucKdes. In this chapter, the principles and instrumentation of accelerator mass spectrometry (AMS), the key player for detection of cosmological radionucKdes in ultra trace scale, will be discussed in detail. Detailed discussion of all the research works carried out to date with cosmogenic radionuclides is out of scope. Only the detection of million-year half-life radionucKdes in ultra trace concentration will be touched, followed by concise description of the required chemistry. Rather than giving a general description, a few of them have been chosen and described in separate sections. Inductively coupled plasma-mass spectrometry (ICP-MS), thermal ionization mass spectrometry (TIMS), secondary ion mass spectrometry (SIMS), or resonant laser ionization mass spectrometer (RIMS), etc. have also been used for detection of cosmogenic radionucKdes. However, these techniques have much lower sensitivity compared to AMS. Brief discussions on these instruments have been appended at the end of this chapter. This chapter ends with a conclusion. 

Kubota, N., Hayashi, S. (2008) State selective detection of sputtered A1 neutrals by resonant laser ionization SNMS. Appl. Surf. ScL, 255,834-836. 

Wendt, K.D.A. The New Generation of Resonant Laser Ionization Mass Spectrometers Becoming Competitive for Selective Atomic Ultra-Trace Determination Eur. J. Mass Spectrom. 2002, 8, 273-285. 

A technique which combines the high sensitivity of resonant laser ionization methods with the advantages of nonlinear coherent Raman spectroscopy is called IDSRS (ionization detected stimulated Raman spectroscopy). The excitation process, illustrated in Figure 5, can be briefly described as a two-step photoexcitation process followed by ion/electron detection. In the first step two intense narrow-band lasers (ct L, 0) ) are used to vibrationally excite the molecule via the stimulated Raman process. The excited molecules are then selectively ionized in a second step via a two- or multiphoton process. If there are intermediate resonant states involved (as state c in Figure 5), the method is called REMPI (resonance enhanced multi-photon ionization)-detected stimulated Raman spectroscopy. The technique allows an increase in sensitivity of over three orders of magnitude because ions can be detected with much higher sensitivity than photons. 

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