Photoionization mass spectrometers

Most of the studies in this decade were carried out with conventional single source mass spectrometers, which limited the kind and accuracy of the information. During the next decade, however, various sophisticated techniques for the study of ion—molecule reactions, such as tandem mass spectrometers, photoionization sources, pulsed sources, flowing afterglow and drift tube methods, crossed and merging beams and ion cyclotron resonance, have been developed. Much detailed information on various aspects of ion—molecule reactions has accumulated, and this has consequently stimulated the theoretical studies as well. This decade was, so to speak, the second epoch in the history of ion—molecule studies. 

The gas beam is skimmed by a conical skimmer before entering the photoionization region of a quadrupole mass spectrometer. Photoionization sampling of the photoproducts takes place s Scm from the nozzle tip. Similar to previous observations [44, 49, 50, 140, 151], the C2H2, C2H2S, ... 

A connnon feature of all mass spectrometers is the need to generate ions. Over the years a variety of ion sources have been developed. The physical chemistry and chemical physics communities have generally worked on gaseous and/or relatively volatile samples and thus have relied extensively on the two traditional ionization methods, electron ionization (El) and photoionization (PI). Other ionization sources, developed principally for analytical work, have recently started to be used in physical chemistry research. These include fast-atom bombardment (FAB), matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ES). 

Time-of-flight mass spectrometers have been used as detectors in a wider variety of experiments tlian any other mass spectrometer. This is especially true of spectroscopic applications, many of which are discussed in this encyclopedia. Unlike the other instruments described in this chapter, the TOP mass spectrometer is usually used for one purpose, to acquire the mass spectrum of a compound. They caimot generally be used for the kinds of ion-molecule chemistry discussed in this chapter, or structural characterization experiments such as collision-induced dissociation. Plowever, they are easily used as detectors for spectroscopic applications such as multi-photoionization (for the spectroscopy of molecular excited states) [38], zero kinetic energy electron spectroscopy [39] (ZEKE, for the precise measurement of ionization energies) and comcidence measurements (such as photoelectron-photoion coincidence spectroscopy [40] for the measurement of ion fragmentation breakdown diagrams). 

In Surface Analysis by Laser Ionization (SALI), a probe beam such as an ion beam, electron beam, or laser is directed onto a surfiice to remove a sample of material. An untuned, high-intensity laser beam passes parallel and close to but above the sur-fiice. The laser has sufficient intensity to induce a high degree of nonresonant, and hence nonselective, photoionization of the vaporized sample of material within the laser beam. The nonselectively ionized sample is then subjected to mass spectral analysis to determine the nature of the unknown species. SALI spectra accurately reflect the surface composition, and the use of time-of-flight mass spectrometers provides fast, efficient and extremely sensitive analysis. 

Cool, T.A. et al., Photoionization mass spectrometer for studies of flame chemistry with a synchrotron light source. Rev. Sci. lustrum., 76,094102,2005. 

Photoionization ti me-of-fli ght mass spectrometry is almost exclusively the method used in chemical reaction studies. The mass spectrometers, detectors and electronics are almost identical. A major distinction is the choice of ionizing frequency and intensity. For many stable molecules multi photon ionization allowed for almost unit detection efficiency with controllable fragmentation(20). For cluster systems this has been more difficult because high laser intensities generally cause extensive dissociation of neutrals and ions(21). This has forced the use of single photon ionization. This works very well for low i oni zati on potential metals ( < 7.87 eV) if the intensity is kept fairly low. In fact for most systems the ionizing laser must be attenuated. A few very small... 

Photoionization of difluorine and chlorine monofluoride appeared to give an even lower value (68), but a reexamination showed that one of the dissociation processes had been ignored (29). In this method fluorine is exposed to monochromatic UV radiation, and the positive and negative ions are observed in a mass spectrometer. 

Atkinson, R., B. J. Finlayson, and J. N. Pitts, Jr. Photoionization mass spectrometer studies of gas phase ozone-olefin reactions. J. Amer. Chem. Soc. 95 7592-7599, 1973. 

The development of lasers has opened up several new techniques for monitoring pollutants in the atmosphere. Sensitivities down to the parts-per-billion range are claimed, and continuous monitoring is possible. The photoionization mass spectrometer has been developed as a sensitive detector for fi radicals in the gas phase. A high-resolution mass spectrometer coupled to a computer is capable of detecting up to 300 compounds in air, both in particulate form and in the gas phase. 

In atmospheric pressure ionization sources (API) the ions are first formed at atmospheric pressure and then transferred into the vacuum. In addition, some API sources are capable of ionizing neutral molecules in solution or in the gas phase prior to ion transfer to the mass spectrometer. Because no liquid is introduced into the mass spectrometer these sources are particularly attractive for the coupling of liquid chromatography with mass spectrometry. Pneumatically assisted electrospray (ESI), atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization (APPI) are the most widely used techniques. 

In several studies, we have combined TRPD data with results obtained over a broader energy range by the time-resolved photoionization mass spectrometer (TPIMS) technique of Lifshitz s group," which is not fully energy resolved but provides a successful complementary technique to TRPD, as shown in the examples below. 

The photoionization efficiency is defined as the number of ions, produced by one incident photon on unit path length at unit gas pressure. The curves in Figures 3-6 represent spectral efficiency curves. On them the ratio of the measured photocurrent to the number of incident monochromatic photons is plotted as function of the photon energy (in e.v.). At the low pressure used in the mass spectrometer (< 10 3 torr) the efficiency curves are proportional to the photoionization cross-section curves.3... 

Fig. 2. Mass spectrometer with photoionization 1—built-in hydrogen lamp 2—vacuum monochromator filled with hydrogen 3—LiF window 4—ionic source container 5—photoionization space with the accelerating grids 6—fluorescent layer for intensity calibration of the incident u.v. light 7—photomultiplier 8—magnetic mass analyzer 9—electron multiplier.

In this connection investigations are to be mentioned in which a mass-spectrometric analysis has been made of neutral radicals, e.g., CHjCO, split off from acetone by u.v. photons in the ordinary range.27-28 In the first a flash lamp has been used and the radicals were ionized as usual by electron impact. In the second the same radical ionized at a field emission electrode. Recently, several alkyl radicals generated by pyrolysis have been studied. Their values of lv and of the photoionization cross sections could be obtained in the mass spectrometer under monochromatic vacuum u.v. irradiation.29... 

The apparatus has been already described in Ref. [7]. The clusters are produced by laser vaporization of a sodium rod, with helium at about 5 bars as a carrier gas and a small amount of SF6. The repetition rate is 10 Hz. In this configuration, the vibrationnal temperature of the formed clusters is roughly 400 K,[10] that gives 85% of C2V geometry and 15% of C3V for a Boltzman distribution. The laser beams are focused onto the cluster beam between the first two plates of an axial Wiley Mac-Laren Time-Of-Flight mass spectrometer with a reflectron. The photoionization efficiency curve as well as the photoabsorption spectrum determined by a photodepletion experiement are displayed on Fig. 1(b) and 1(c) respectively. The ionization threshold is at 4.3 eV, close to the 4.4 eV calculated for the C3V isomer and 4.9 eV for the C2V isomer (see the Fig. 1 (b)). The conclusion arising out of the photodepletion spectrum shown on Fig 1(c) and from ab initio calculations of the excited states, [5] is that the observed... 

For pump-probe photoionization (PPI, Fig.l) the first laser pulse is tuned into resonance with the (vibrationless) electronic transition of the molecule, the second pulse is red-shifted in wavelength, so that the enhanced (1+1 ) photoion signal can be easily identified. When a time-of-flight mass spectrometer is used for detection the mass-selective photoion signal as a function of time delay can be recorded as the RCS spectrum of the electronically excited state, which is particularly useful for the specific investigation of molecular clusters. 

Figure 1. Experimental set-up for performing transient two-photon ionization spectroscopy on metal clusters. The particles were produced in a seeded beam expansion, their flux detected with a Langmuir-Taylor detector (LTD). The pump and probe laser pulses excited and ionized the beam particles. The photoions were size selectively recorded in a quadrupole mass spectrometer (QMS) and detected with a secondary electron multiplier (SEM). The signals were then recorded as a function of delay between pump and probe pulse.

The complications just described can be minimized if there is greater selectivity in the ionization process, as is sometime possible when photoionization is used as the excitation mechanism. Because the ionization energy can be more precisely controlled, it is possible in selected cases to produce only the desired reactant-ion species, or at least to minimize production of other ions. As already noted in the earlier section on formation of excited ions, it is also possible to populate specific internal-energy states of some reactant ions by using a photoionization source. One of the earliest photoionization mass spectrometers used to study interaction of internally excited ions with neutrals was that constructed by Chupka et al.91 Such apparatuses typically incorporate a photon source (either a line or a continuum source) and an optical monochromator, which are coupled to the reaction chamber. Various types of mass analyzer, including sector type, time-of-flight (TOF), and quadrupole mass filters, have been used with these apparatuses. Chupka has described the basic instrumental configuration in some detail.854 Photoionization mass spectrometers employed to study interactions of excited ions with neutral species have also been constructed in several other laboratories.80,1144,142,143 The apparatus recently developed by LeBreton et al.80 is illustrated schematically in Fig. 7 and is typical of such instrumentation. 

Figure 7. Schematic diagram of photoionization mass spectrometer. Axis of quadrupole mass spectrometer is parallel to exit slit of monochromator mass spectrometer has been rotated 90° for purposes of illustration here.80...

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