Ion fragmentation

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). 

SIMS is, strictly speaking, a destructive teclmique, but not necessarily a damaging one. In the dynamic mode, used for making concentration depth profiles, several tens of monolayers are removed per minute. In static SIMS, however, the rate of removal corresponds to one monolayer per several hours, implying that the surface structure does not change during the measurement (between seconds and minutes). In this case one can be sure that the molecular ion fragments are truly indicative of the chemical structure on the surface. 

It is well known that the electron-impact ionization mass spectrum contains both the parent and fragment ions. The observed fragmentation pattern can be usefiil in identifying the parent molecule. This ion fragmentation also occurs with mass spectrometric detection of reaction products and can cause problems with identification of the products. This problem can be exacerbated in the mass spectrometric detection of reaction products because diese internally excited molecules can have very different fragmentation patterns than themial molecules. The parent molecules associated with the various fragment ions can usually be sorted out by comparison of the angular distributions of the detected ions [8]. 

The spectra of alkylarylthiazoles generally possess fragmentation patterns similar to those previously mentioned for alkyl- and arylthiazoles. In this case, scission of the S-Cj and C3-C4 bonds of the thiazole ring can occur in ion fragments as well as in the molecular ion (124). 

The steps (reactions) by which normal ions fragment are important pieces of information that are lacking in a normal mass spectrum. These fragmentation reactions can be deduced by observations on metastable ions to obtain important data on molecular structure, the complexities of mixtures, and the presence of trace impurities. 

In a B /E-linked scan, a product ion (fragment ion) is selected. In this case it is m4, which can be any fragment ion but not a molecular ion (connects with itself). All precursor ions (m, mj, m3), which decompose to give the product ion m4, are found, giving connections m -m4, m2-m4, m3-m4. Any one of the precursor ions could be a molecular ion. 

Again, as for metastable ions, linked scanning of the first and third quadrupoles reveals important information on fragmentation processes, viz., which normal ions fragment to give which product ions. 

Two explanations were suggested for the great intensity of the peaks due to oxygen-containing positive ion fragments relative to the original hydrocarbon... 

Product ion/daughter ion An ion related to a precursor or parent ion by a process such as fragmentation. For example, a parent ion fragments to produce a daughter ion. 

Mass Spectra and Chemical Structure While there are a number of books (Refs 16, 30, 49 64) already referred to, which deal with details of the instrumentation and techniques of mass spectrometry, there are several concise introductory texts (Refs 10, 21 52) on the interpretation of mass spectra. Still other recent books deal comprehensively with organic structural investigation by mass spectrometry. One of these (Ref 63) discusses fundamentals of ion fragmentation mechanisms, while the others (Refs 7, 15, 20, 28 29) describe mass spectra of various classes of organic compounds. In the alloted space for this article methods of interpretation of mass spectra and structural identification can not be described in depth. An attempt is, therefore, made only to briefly outline the procedures used in this interpretation... 

The apparatus for the PFAM film coating on the slider surface is shown in Fig. 1 (a). The film thickness was measured by the TOF-SIMS as shown in Fig. 1 (b). It used a pulsed primary Ga+ ion beam to impact the surface of the PFAM film with an inset energy of 15 keV, an extractor current of 2 fj,A, beam current of 600 pA, a pulse width of 17.5 ns, and a frequency of 10 kHz, respectively. The positive TOF-SIMS spectra on the slider surface is shown in Fig. 2 where the peaks at m/z 31, 50, 69, 100, and 131 in Fig. 2(a) correspond to the positive secondary ion fragments of CF+, CFj, C2F4, and C3F5, respectively. The peak at m/z 469 apparent in Fig. 2(b) corresponds to the ion C12H7F 15O2H+ which is the characteristic ion of PFAM molecules. Therefore, the positive TOF-SIMS spectra demonstrates the existence of PFAM film [24,25]. The thickness of the PFAM film can be determined... 

Structure does not change during the measurement. In this case the molecular ion fragments are indicative of the chemical structure of the surface. 

Alternative approaches consist in heat extraction by means of thermal analysis, thermal volatilisation and (laser) desorption techniques, or pyrolysis. In most cases mass spectrometric detection modes are used. Early MS work has focused on thermal desorption of the additives from the bulk polymer, followed by electron impact ionisation (El) [98,100], Cl [100,107] and field ionisation (FI) [100]. These methods are limited in that the polymer additives must be both stable and volatile at the higher temperatures, which is not always the case since many additives are thermally labile. More recently, soft ionisation methods have been applied to the analysis of additives from bulk polymeric material. These ionisation methods include FAB [100] and LD [97,108], which may provide qualitative information with minimal sample pretreatment. A comparison with FAB [97] has shown that LD Fourier transform ion cyclotron resonance (LD-FTTCR) is superior for polymer additive identification by giving less molecular ion fragmentation. While PyGC-MS is a much-used tool for the analysis of rubber compounds (both for the characterisation of the polymer and additives), as shown in Section 2.2, its usefulness for the in situ in-polymer additive analysis is equally acknowledged. 

LD), in which flash vaporisation of the sample is induced, may be applied. Other techniques which permit detection of less-volatile chemical species are FD (with simultaneous desorption/ionisation of molecules), FAB (with the sample dissolved (dispersed) in a suitable liquid) and SIMS (based on bombardment of a solid surface with high-energy ions). LD-FUCR-MS is superior to FAB-MS for polymer/additive identification because it gives molecular ion fragmentation [83],... 

Databases Commercially molecular ions, fragment ions pos./neg. mode Only user-generated... 

The Lozier tube, illustrated in Figure 3, has been used by several groups for a variety of different studies, including the determination of appearance energies and kinetic energies of ion fragments produced in electron impact-induced dissociation... 

---