Electron-impact

Electron impact (El) is probably the most widely used technique for ionization in MS. It is characterized by a high sensitivity, reproducibility and stability. The ionization is based on thermally produced electrons, which orthogonally cross the analyte stream and create mainly positive ions by extracting electrons from the analyte molecules (Fig. 7). 

The resulting spectra from El usually contain a number of fragments, providing extensive structural information about the analyte. A disadvantage of the observed fragmentation is eventually occurring isobaric overlay from different compounds in the analysis of sample mixtures, which often requires a separation step prior to the MS analysis. For this purpose the coupling of a GC with the ion source of the mass spectrometer via capillary inlet is a well established technique. Volatiles can be selectively introduced into El mass spectrometers via pervaporation membranes. The principle and application of this technique, called membrane introduction (MI) MS was recently reviewed [45]. The accuracy of intensity ratio measurements by El MS is about 0.1 -0.5% [4,8]. 

A specific variant of El MS is isotope ratio (IR) MS [46]. It is based on electron impact ionization with maximized ionization probability. IR MS is limited to the analysis of gases of high volatility and low reactivity such as CO2, N2 or SO2. The analytes of interest thus have to be transformed into one of these gases before introduction into the IR MS. Information on the position of C labelings in the analyte can be only obtained, if all carbons are isolated position specific and subsequently combusted. In this context Corso and Brenna [47] showed position specific analysis by IR MS for methylpalmitate through pyrolytic fragmentation. IR MS exhibits an extremely high precision of 0.00001 % for the isotope ratio measurement and is optimal to quantify low label enrichments [48]. This is especially important for in vivo studies with ani- 

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CELS, EIS Characteristic-energy-loss spectroscopy, electron-impact spectroscopy [128] Same as EELS Same as EELS... 

The Artis fonned from Ar +Ar, where the metastable Ar is a product of electron-impact or charge-transfer... 

Electron-impact energy-loss spectroscopy (EELS) differs from other electron spectroscopies in that it is possible to observe transitions to states below the first ionization edge electronic transitions to excited states of the neutral, vibrational and even rotational transitions can be observed. This is a consequence of the detected electrons not originating in the sample. Conversely, there is a problem when electron impact induces an ionizing transition. For each such event there are two outgoing electrons. To precisely account for the energy deposited in the target, the two electrons must be measured in coincidence. 

Coincidence experiments explicitly require knowledge of the time correlation between two events. Consider the example of electron impact ionization of an atom, figure Bl.10.7. A single incident electron strikes a target atom or molecule and ejects an electron from it. The incident electron is deflected by the collision and is identified as the scattered electron. Since the scattered and ejected electrons arise from the same event, there is a time correlation... 

Figure Bl.10.7. Electron impact ionization coincidence experiment. The experiment consists of a source of incident electrons, a target gas sample and two electron detectors, one for the scattered electron, the other for the ejected electron. The detectors are coimected tlirough preamplifiers to the inputs (start and stop) of a time-to-amplitiide converter (TAC). The output of the TAC goes to a pulse-height-analyser (PHA) and then to a nuiltichaimel analyser (MCA) or computer.

Figure Bl.10.11. Electron impact double ionization triple coincidence experiment. Shown are the source of electrons, target gas, tluee electron detectors, one for the scattered electron and one for each of the ejected...

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 probability for a particular electron collision process to occur is expressed in tenns of the corresponding electron-impact cross section n which is a function of the energy of the colliding electron. All inelastic electron collision processes have a minimum energy (tlireshold) below which the process cannot occur for reasons of energy conservation. In plasmas, the electrons are not mono-energetic, but have an energy or velocity distribution,/(v). In those cases, it is often convenient to define a rate coefficient /cfor each two-body collision process ... 

A wide variety of metliods has been used to pump laser systems. Altliough optical pumping has been implied, tliere is an array of collisionally or electron impact pumped systems, as well as electrically pumped metliods. The efficiency of tire pumping cycle in many ways defines tire utility and applications of each scheme. The first... 

Veprek S and Sarott F A 1982 Electron-impact-induced anisotropic etching of silicon by hydrogen Plasma Chem. Plasma Proc. 2 233-46... 

The base peak in the mass spectrum of the LM free metal-ligand ion and the fragmentation patterns of this parent ion are of particuliar significance since they illustrate the effect of coordination upon the properties of the thiazole ligand. The free thiazole fragments upon electron impact by two major routes (Scheme 86 also cf. Section II. 6). 

We say the molecule AB has been ionized by electron impact The species that results called the molecular ion, is positively charged and has an odd number of electrons—it IS a cation radical The molecular ion has the same mass (less the negligible mass of a single electron) as the molecule from which it is formed... 

Unlike the case of benzene in which ionization involves loss of a tt electron from the ring electron impact induced ionization of chlorobenzene involves loss of an elec tron from an unshared pair of chlorine The molecular ion then fragments by carbon-chlorine bond cleavage... 

Understanding how molecules fragment upon electron impact permits a mass spec trum to be analyzed m sufficient detail to deduce the structure of an unknown compound Thousands of compounds of known structure have been examined by mass spectrome try and the fragmentation patterns that characterize different classes are well docu mented As various groups are covered m subsequent chapters aspects of their fragmentation behavior under conditions of electron impact will be descnbed... 

Section 13 22 Mass spectrometry exploits the information obtained when a molecule is ionized by electron impact and then dissociates to smaller fragments Pos itive ions are separated and detected according to their mass to charge (m/z) ratio By examining the fragments and by knowing how classes of molecules dissociate on electron impact one can deduce the structure of a compound Mass spectrometry is quite sensitive as little as 10 g of compound is sufficient for analysis... 

Molecular Identification. In the identification of a compound, the most important information is the molecular weight. The mass spectrometer is able to provide this information, often to four decimal places. One assumes that no ions heavier than the molecular ion form when using electron-impact ionization. The chemical ionization spectrum will often show a cluster around the nominal molecular weight. 

The mass spectrum is a fingerprint for each compound because no two molecules are fragmented and ionized in exactly the same manner on electron-impact ionization. In reporting mass spectra the data are normalized by assigning the most intense peak (denoted as base peak) a value of 100. Other peaks are reported as percentages of the base peak. 

Thus two electrons exit the reaction zone, leaving a positively charged species (M ) called an ion (in this case, a molecular ion). Strictly, M" is a radical-cation. This electron/molecule interaction (or collision) was once called electron impact (also El), although no impact actually occurs. 

Molecules can interact with energetic electrons to give ions (electron ionization, El), which are electrically charged entities. The interaction used to be called electron impact (also El), although no actual collision occurs. 

Electrons and photons do not impact molecules or atoms. They interact with them in ways that result in various electronic excitations, including ionization. For this reason it is recommended that the terms electron impact and photon impact be avoided. 

Field, F.H. and Franklin, J.L., Electron Impact Phenomena, Academic Press, New York, 1957. 

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