The Ionization Process

This chapter should be read in conjunction with Chapter 3, Electron Ionization. In electron ionization (El), a high vacuum (low pressure), typically 10 mbar, is maintained in the ion source so that any molecular ions (M +) formed initially from the interaction of an electron beam and molecules (M) do not collide with any other molecules before being expelled from the ion source into the mass spectrometer analyzer (see Chapters 24 through 27, which deal with ion optics). 

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Acetic acid and other carboxylic acids are protonated in superacids to form stable carboxonium ions at low temperatures. Cleavage to related acyl cations is observed (by NMR) upon raising the temperature of the solutions. In excess superacids a diprotonation equilibrium, indicated by theoretical calculations, can play a role in the ionization process. 

Although there has been some controversy concerning the processes involved in field ionization mass spectrometry, the general principles appear to be understood. Firstly, the ionization process itself produces little excess of vibrational and rotational energy in the ions, and, consequently, fragmentation is limited or nonexistent. This ionization process is one of the mild or soft methods available for producing excellent molecular mass information. The initially formed ions are either simple radical cations or radical anions (M ). 

For a more detailed description of the ionization process inherent in electrospray, please see Chapter 9, which discusses atmospheric pressure ionization (API), The reader also should compare electrospray with thermospray (see Chapter 11). 

The process of field ionization presupposes that the substance under investigation has been volatilized by heat, so some molecules of vapor settle onto the tips held at high potential. In such circumstances, thermally labile substances still cannot be examined, even though the ionization process itself is mild. To get around this difficulty, a solution of the substance under investigation can be placed on the wire and the solvent allowed to evaporate. When an electric potential is applied, positive or negative ions are produced, but no heating is necessary to volatilize the substance. This technique is called field desorption (FD) ionization. 

Figure 9.50(a) illustrates the ionization process in a UPS experiment. In this type of experiment the incident radiation always has much more energy than is necessary to ionize the molecule M into either the zero-point level or a vibrationally excited level of M. The excess energy is then removed as kinetic energy of the photoelectron. 

Instead of using a laser operating in the vacuum-ultraviolet region a laser operating at half the energy may be used. Then the ionization process in Figure 9.50(b) involves the... 

Because of the complex situation on the surface, satisfactory theoretical description of the ionization process leading to secondary ion formation has not yet been possible. Different ionization mechanisms have been proposed ... 

SNMS sensitivity depends on the efficiency of the ionization process. SNs are post-ionized (to SN" ) either hy electron impact (El) with electrons from a hroad electron (e-)heam or a high-frequency (HF-) plasma (i.e. an e-gas), or, most efficiently, hy photons from a laser. In particular, the photoionization process enables adjustment of the fragmentation rate of sputtered molecules by varying the laser intensity, pulse width, and/or wavelength. 

Surface analysis by non-resonant (NR-) laser-SNMS [3.102-3.106] has been used to improve ionization efficiency while retaining the advantages of probing the neutral component. In NR-laser-SNMS, an intense laser beam is used to ionize, non-selec-tively, all atoms and molecules within the volume intersected by the laser beam (Eig. 3.40b). With sufficient laser power density it is possible to saturate the ionization process. Eor NR-laser-SNMS adequate power densities are typically achieved in a small volume only at the focus of the laser beam. This limits sensitivity and leads to problems with quantification, because of the differences between the effective ionization volumes of different elements. The non-resonant post-ionization technique provides rapid, multi-element, and molecular survey measurements with significantly improved ionization efficiency over SIMS, although it still suffers from isoba-ric interferences. 

As illustrated in Fig. 3.41, several laser schemes can be used to ionize elements and molecules. Scheme (a) in this figure stands for non-resonant ionization. Because the ionization cross-section is very low, a very high laser intensity is required to saturate the ionization process. Scheme (b) shows a simple single-resonance scheme. This is the simplest but not necessarily the most desirable scheme for resonant post-ionization. Cross-... 

Molecular particles can dissociate during the ionization process. This is taken into account by the different indices i and j. 

Typical ion sources employ a noble gas (usually Ar). The ionization process works either by electron impact or within a plasma created by a discharge the ions are then extracted from the region in which they are created. The ions are then accelerated and focused with two or more electrostatic lenses. These ion guns are normally operated to produce ions of 0.5-10 keV energy at currents between 1 and 10 pA (or, for a duoplasmatron, up to 20 pA). The chosen spot size varies between 100 pm and 5 mm in diameter. 

There is some small print to the derivation the orbitals must not change during the ionization process. In other words, the orbitals for the cation produced must be the same as the orbitals for the parent molecule. Koopmans (1934) derived the result for an exact HF wavefunction in the numerical Hartree-Fock sense. It turns out that the result is also valid for wavefunctions calculated using the LCAO version of HF theory. 

Arrecognizes that in the infinitely dilute solution HC1 is already completely separated into ions so that no enthalpy change is involved in the ionization process. 

If no transfer of translational energy occurs, then the charge exchange process probably takes place when the distance between the ion and the molecule is large. This means, however, that the ion and the molecule can be considered as isolated from each other, and therefore, the recombination process of the ion and the ionization process of the molecule must obey the spectroscopic transition laws. On the other hand, if a large transfer of translational energy takes place, then the process probably takes place when the distance is small, and possibly then all selection rules break down. 

We conclude, that the ionization processes by charge exchange in a perpendicular type apparatus or using electron impact at high energy are substantially similar, and therefore it is possible to calculate the electron impact mass spectrum from charge exchange observations by... 

The ionization process can be described as a one-particle event, when only one term dominates in summation (3), yielding a pole strength close unity. In this case, 1 - Fu gives an estimate of the fraction of photoemission intensity dispersed in many-body effects. On the contrary, small pole strengths are indicative (18-20) of a breakdown of the one-particle picture of ionization. 

When this analysis was first attempted [9-11] very few values of 1 had been obtained from series limits in the third spectra of the lanthanides, and the first comprehensive sets were calculated from Born-Haber cycles [9]. Subsequent spectroscopic values [12] confirmed the early work and are plotted in Eig. 1.1. In all cases they refer to the ionization process... 

Knowing that the energy cost of removing core electrons is always excessive, we can predict that the ionization process will stop when all valence electrons have been removed. Thus, a knowledge of ground-state configurations is all that we need to make qualitative predictions about cation stability. 

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