Photoionization reviews

Here we present new data on various ion-molecule reactions occurring in the radiolysis and photoionization of hydrocarbons. We will also review some earlier findings which will illustrate the kind of information which can be derived from the approach mentioned above. 

Methane-to-methanol conversion by gas-phase transition metal oxide cations has been extensively studied by experiment and theory see reviews by Schroder, Schwarz, and co-workers [18, 23, 134, 135] and by Metz [25, 136]. We have used photofragment spectroscopy to study the electronic spectroscopy of FeO" " [47, 137], NiO [25], and PtO [68], as well as the electronic and vibrational spectroscopy of intermediates of the FeO - - CH4 reaction. [45, 136] We have also used photoionization of FeO to characterize low lying, low spin electronic states of FeO [39]. Our results on the iron-containing molecules are presented in this section. 

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. 

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... 

The significance of the development of photoelectron spectroscopy over the last decade for a better understanding of solid surfaces, adsorption, surface reactivity, and heterogeneous catalysis has been discussed. The review is illustrative rather than exhaustive, but nevertheless it is clear that during this period XPS and UPS have matured into well-accepted experimental methods capable of providing chemical information at the molecular level down to 10% or less of a monolayer. The information in its most rudimentary state provides a qualitative model of the surface at a more sophisticated level quantitative estimates are possible of the concentration of surface species by making use of escape depth and photoionization cross-section data obtained either empirically or by calculation. 

Spark, photoionization, surface, thermionic, and laser ionization sources are not considered in this review. 

Finally, solute radical ions can be generated by light-induced, one-photon or multiphoton ionization of their parent compounds (Chaps. 5 and 16). This approach is particularly useful in the ultrafast studies of short-lived, unstable radical ions that aim to unravel their solvation, recombination, reaction, and vibrational relaxation dynamics of the primary charges (see, e.g., Chap. 10). Whereas the time scale of radiolytic production of secondary ions is always limited by the rate with which the primary species reacts with the dispersed parent molecules, light-induced charge separation can occur in <100 fsec. There are many studies on photoionization of solute molecules in liquid solutions we do not intend to review these works. 

We have included a discussion of some aspects of the theory of photoionization in this review because it is a simple photochemical reaction and so as to show the extent to which crude detailed calculations reproduce experimental data for the case of a simple photochemical reaction. 

For the purposes of this review it is convenient to focus attention on that class of molecules in which the valence electrons are easily distinguished from the core electrons (e.g., -n electron systems) and which have a large number of vibrational degrees of freedom. There have been several studies of the photoionization of aromatic molecules.206-209 In the earliest calculations either a free electron model, or a molecule-centered expansion in plane waves, or coulomb functions, has been used. Only the recent calculation by Johnson and Rice210 explicitly considered the interference effects which must accompany any process in a system with interatomic spacings and electron wavelength of comparable magnitude. The importance of atomic interference effects in the representation of molecular continuum states has been emphasized by Cohen and Fano,211 but, as far as we know, only the Johnson-Rice calculation incorporates this phenomenon in a detailed analysis. 

Nitric oxide is also present in the upper atmosphere its role has been reviewed by Nicolet.326-328 Because of solar radiation, important processes are photoionization, photodissociation, and the formation of electronically excited levels. The continuum seen in the night airglow has often been ascribed to reaction (4). However, both the y and / bands of NO are absent in the night airglow. Since the / and y emissions arise from... 

Additional details on some of these methods are described in other sections of this review. Attempts have also been made to determine excited-state populations in single-source mass-spectrometric experiments from an analysis of ionization efficiency curves.38ad There are several difficulties in applying such methods. For instance, it is now known from photoionization studies that ionization processes may be dominated by autoionization. Therefore, the onset of a new excited state is not necessarily characterized by an increased slope in the electron-impact ionization-efficiency curve, which is proportional to the probability of producing that state, as had been assumed earlier. Another problem arises because of the different radiative lifetimes that are characteristic of various excited ionic states (see Section I.A.4). 

Fig. 7.9. The positronium source and laser interaction region used by Fee and coworkers. A magnetic field of 100 G (0.01 T) guides the incident beam onto the target and also transports the positrons liberated from the photoionized 2S positronium to the detector. Reprinted from Physical Review Letters 70, Fee et al, Measurement of the positronium 13Si-23Si interval by continuous wave two-photon excitation, 1397-1400, copyright 1993 by the American Physical Society.

To date, since the photoelectron spectroscopy of doped fullerenes has been difficult to perform, numerous theoretical studies of photoionization spectra of atoms encaged in doped fullerenes, performed at various levels of approximations, [15-46], have been prevalent. Consequently, to aid emerging experiments and new theories on gas phase doped fullerenes, a review of the theoretical findings and predictions that have been accumulated in this area of research so far is very timely. This is precisely the aim of the present paper. 

Ultracold neutral plasmas may be produced by laser cooling and trapping of different types of neutral atoms [105] such as calcium, strontium, rubidium, cesium etc., by photoionizing Bose condensates [106] and also by spontaneous ionization of dense Rydberg atoms [107,108]. A review on ultracold neutral plasmas due to Killan et al. [61] gives an excellent disposition on the subject. 

J. W. Rabalais, Principles of Ultraviolet Photoelectron spectroscopy, Wiley, New York, 1977, is mentioned among the numerous monographs because of its literature review and the lucid presentation of difficult topics, such as photoionization cross-sections. 

The applications of lasers in kinetic studies are essentially twofold. Firstly, they can be used to produce a particular species. This might be a vibration—rotationally defined quantum state of a molecule [21], or it could be an ion [22—24] or fragment [25—28] produced by photoionization or photodissociation [29, 30] of some parent. The combination of specific frequency, short pulse duration and high powers makes selective control of chemical reactions possible. Secondly, they can be used as detectors of specific species and quantum states [31, 32]. There are a number of different methods of using lasers to detect small concentrations of a species in a chemical reaction. Lin and McDonald [33] have broadly reviewed the generation and detection of reactive species in static systems with particular emphasis on the use of lasers for this purpose. 

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