Resonance photoionization spectroscopy

R. Zhao, l.M. Konen, R.N. Zare, Optical-optical double resonance photoionization spectroscopy of nf Rydberg states of nitric oxide. J. Chem. Phys. 121, 9938 (2004)... 

S.V. Andreev, V.S. Letokhov, V.I. Mishin Laser resonance photoionization spectroscopy of Rydberg levels in Fr. Phys. Rev. Lett. 59, 1274 (1987)... 

Photoionization detection in a buffer gas has also been used to study the properties of superheavy (transuranium) elements with charge numbers Z > 92. Isotopes of such elements can only be produced by fission reactions in heavy-ion collisions or by transfer reactions using radioactive targets. The elements produced can be placed in an optical buffer-gas cell for the purpose of laser resonance photoionization spectroscopy. This was successfully demonstrated with atoms of such radioactive elements as americium (Z = 95) (Backe et al. 2000), einsteinium (Z = 99) (Kohler et al. 1997), and fermium (Z = 100) (Sewtz et al. 2003). 

Photoelectron spectroscopy of free radicals has been utilized for detection of radicals. It can be via resonance photoexcitation and photoionization (e.g. ZEKE) or non-resonance photoionization (e.g. single-photon VUV photoionization). The photoelectron spectroscopy of free radicals has been reviewed in 1994 by Chen.5 A recent review on mass spectrometry, photoelectron spectroscopy, and photoionization of free radicals by Sablier and Fujii is available.72 It is worthwhile to point out that mass spectrometry by photoionization offers some advantage for the detection of radicals, in comparison with the conventional mass spectroscopy by electron-impact... 

Brouwer and Wilbrandt have applied resonance Raman spectroscopy and calculations to questions of structure of amine radical cations [73]. Well-resolved Raman spectra of trialkylamine radical cations that are so short-lived that their electrochemical oxidation waves are irreversible may be obtained at room temperature in solution by photoionization and time-resolved detection. Comparison of the observed spectrum with calculations for various isomers provides a powerful method of answering structural questions. Density-functional calculations prove much easier to apply to open-shell species than Hartree-Fock calculations, which require cumbersome and expensive corrections to introduce suffieient electron correlation to eonsider questions like the charge distribution of disubstituted piperazine (1,4-diazacyclohexane) radical cations. The dimethyl- and diphenyl-substituted piperazine radical cations are delocalized, but charge is localized on one ArN unit of the dianisyl-substituted compound [73dj. 

This operation correlates the ground and excited states on both surfaces. The two-level charge-induced interchange of the conformers can occur on a timescale of a few picoseconds, which is typical for the resonant photoionization process [35], The dynamics of such a process, 0)° -> 1)+1 and 1)° -> 0)+1, is monitored in real time by the change in the anchoring A-N stretch, equal to Av(Au-N) = 145, 165 (due to the appearance of the A-N stretch doublet), and by the disappearance of the vibrational mode -v(N-H - N) (see Table 3) using, e.g. time-resolved picosecond UV/IR pump-probe ionization depletion spectroscopy [35]. 

Femtosecond photodissociation dynamics of nitroethane and l-nitropropane have been studied in the gas phase and in solution by resonance Raman spectroscopy, with excitation in the absorption band around 200 nm. At such short time-scales it is possible to detect changes in the two N-O bond lengths in the Franck-Condon region, prior to C-N bond cleavage. Photolyses of nitroalkanes at 193 nm have been monitored by photoionization of the fragments and time-of-flight mass spectrometry. Both C-N and N-O bond dissociation pathways are observed and, under the conditions of free jet expansion, primary products such as pentyl and hexyl radicals are stabilized and can be detected. 

A number of less commonly used analytical techniques are available for determining PAHs. These include synchronous luminescence spectroscopy (SLS), resonant (R)/nonresonant (NR)-synchronous scan luminescence (SSL) spectrometry, room temperature phosphorescence (RTP), ultraviolet-resonance Raman spectroscopy (UV-RRS), x-ray excited optical luminescence spectroscopy (XEOL), laser-induced molecular fluorescence (LIMP), supersonic jet/laser induced fluorescence (SSJ/LIF), low- temperature fluorescence spectroscopy (LTFS), high-resolution low-temperature spectrofluorometry, low-temperature molecular luminescence spectrometry (LT-MLS), and supersonic jet spectroscopy/capillary supercritical fluid chromatography (SJS/SFC) Asher 1984 Garrigues and Ewald 1987 Goates et al. 1989 Jones et al. 1988 Lai et al. 1990 Lamotte et al. 1985 Lin et al. 1991 Popl et al. 1975 Richardson and Ando 1977 Saber et al. 1991 Vo-Dinh et al. 1984 Vo- Dinh and Abbott 1984 Vo-Dinh 1981 Woo et al. 1980). More recent methods for the determination of PAHs in environmental samples include GC-MS with stable isotope dilution calibration (Bushby et al. 1993), capillary electrophoresis with UV-laser excited fluorescence detection (Nie et al. 1993), and laser desorption laser photoionization time-of-flight mass spectrometry of direct determination of PAH in solid waste matrices (Dale et al. 1993). 

Although most suitable for use with lasers, Thermionic diodes have also been successfully applied to synchrotron radiation studies by using wiggler magnets to enhance the intensity of the beam [390]. Last but not least, one should mention the important category of atomic beam experiments, complemented by the techniques of photoelectron and photoion spectroscopy. All these techniques are suitable for the experimental study of interacting resonances. We turn now to their theoretical description, which will be illustrated by experimental examples. 

As we have seen, collisions are important for the signal generation in LEI. In low-pressure experiments photoionization instead is the principal origin of the signal. The term Resonance Ionization Spectroscopy (RIS) is then frequently used. Several examples of opto-galvanic detection schemes for different atoms are shown in Fig.9.11. If multi-photon excitation of the atoms to be studied is used the technique is referred to as REMPI (REsonance Multi-Photon Ionization) spectroscopy. The selectivity of RIS and REMPI can be further enhanced by using a mass spectrometer to ana-... 

Fig. 9.7 Various resonant photoionization techniques for ultrasensitive spectroscopy of very rare atoms and isotopes (a) ionization of a transverse thermal atomic beam (b) ionization of atoms in a buffer gas (c) ionization of atoms trapped in a hot cavity (d) ionization of...

The high sensitivity of the photoionization method is very useful for the spectroscopy of very rare elements whose spectral properties are not well known. One such element is francium (Fr), the natural abundance of which is extremely low (1 Fr atom is found in 3 X 10 atoms of natural uranium), and which is formed as a result of the decay of In our experiments (Andreyev et al. 1987, 1988), the resonance photoionization technique was used to detect Fr atoms and study their Rydberg states. The atoms... 

Resonant photoemission spectroscopy can give valuable information about the atomic orbital component of the state in the spectra. Figure 10 shows a plot of area intensities of the surface state induced peak for TaC(lll) as a function of the exciting photon energy. In Fig. 10, a cross section of the Ta 5d band observed in the photoemission spectra for poly-Ta (48) is also shown. The photoionization cross section for the surface state on TaC(lll) is resonantly enhanced at hv of 40 and 50 eV, as in the case for the Ta 5d band in poly-Ta. These enhancements of the cross section are well explained by the resonance process that proceeds via photon-induced excitation,... 

The general principle of detection of free radicals is based on the spectroscopy (absorption and emission) and mass spectrometry (ionization) or combination of both. An early review has summarized various techniques to detect small free radicals, particularly diatomic and triatomic species.68 Essentially, the spectroscopy of free radicals provides basic knowledge for the detection of radicals, and the spectroscopy of numerous free radicals has been well characterized (see recent reviews2-4). Two experimental techniques are most popular for spectroscopy studies and thus for detection of radicals laser-induced fluorescence (LIF) and resonance-enhanced multiphoton ionization (REMPI). In the photochemistry studies of free radicals, the intense, tunable and narrow-bandwidth lasers are essential for both the detection (via spectroscopy and photoionization) and the photodissociation of free radicals. 

Laser spectroscopy of the 1S-2S transition has been performed by Mills and coworkers at Bell Laboratories (Chu, Mills and Hall, 1984 Fee et al, 1993a, b) following the first excitation of this transition by Chu and Mills (1982). Apart from various technicalities, the main difference between the 1984 and 1993 measurements was that in the latter a pulse created from a tuned 486 nm continuous-wave laser with a Fabry-Perot power build-up cavity, was used to excite the transition by two-photon Doppler-free absorption, followed by photoionization from the 2S level using an intense pulsed YAG laser doubled to 532 nm. Chu, Mills and Hall (1984), however, employed an intense pulsed 486 nm laser to photoionize the positronium directly by three-photon absorption from the ground state in tuning through the resonance. For reasons outlined by Fee et al. (1993b), it was hoped that the use of a continuous-wave laser to excite the transition would lead to a more accurate determination of the frequency interval than the value 1233 607 218.9 10.7 MHz obtained in the pulsed 486 nm laser experiment (after correction by Danzmann, Fee and Chu, 1989, and adjustment consequent on a recalibration of the Te2 reference line by McIntyre and Hansch, 1986). 

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