Photoionization spectrometer

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... 

The 5950A ESCA spectrometer is interfaced to a desktop computer for data collection and analysis. Six hundred watt monochromatic A1 Ka X-rays are used to excite the photoelectrons and an electron gun set at 2 eV and 0.3 mAmp is used to reduce sample charging. Peak areas are numerically integrated and then divided by the theoretical photoionization cross-sections (11) to obtain relative atomic compositions. For the supported catalyst samples, all binding energies (BE) are referenced to the A1 2p peak at 75.0 eV, the Si 2p peak at 103.0 eV, or the Ti 2p3/2 peak at 458.5 eV. 

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. 

A third source of error is associated with the fragmentation pattern caused by dissociation of the molecular ions formed in the source region of the spectrometer. Under severe conditions these processes may proceed with substantial isotopic fractionation, and this obscures the measurements of isotopic composition at the collector. To some extent careful standardization of the instrumental conditions may ensure that errors from fragmentation are systematic, and thus cancel (at least to some extent). Alternatively, softer ionization methods can be used to prevent most or all of the fragmentation. The bottom spectrum in Fig. 7.7 illustrates this approach it shows the mass spectrum of chlorobenzene obtained by photoionization. Only the parent molecular ions are observed. It should be kept in mind, however, that softer ionization usually yields smaller ion currents and consequently statistical counting errors increase. 

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 prompt appearance of these absorption bands within a nanosecond response time of the kinetic spectrometer (Fig. la,b) is a direct indication that intense 308-nm laser pulses induce photoionization of 2AP [10] ... 

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... 

---