Electron impact ionization characterized

Physical Chemical Characterization. Thiamine, its derivatives, and its degradation products have been fully characterized by spectroscopic methods (9,10). The ultraviolet spectmm of thiamine shows pH-dependent maxima (11). H, and nuclear magnetic resonance spectra show protonation occurs at the 1-nitrogen, and not the 4-amino position (12—14). The H spectmm in D2O shows no resonance for the thiazole 2-hydrogen, as this is acidic and readily exchanged via formation of the thiazole yUd (13) an important intermediate in the biochemical functions of thiamine. Recent work has revised the piC values for the two ionization reactions to 4.8 and 18 respectively (9,10,15). The mass spectmm of thiamine hydrochloride shows no molecular ion under standard electron impact ionization conditions, but fast atom bombardment and chemical ionization allow observation of both an intense peak for the patent cation and its major fragmentation ion, the pyrimidinylmethyl cation (16). 

Additional details on some of these methods are described in other sections of this review. Attempts have also been made to determine excited-state populations in single-source mass-spectrometric experiments from an analysis of ionization efficiency curves.38ad There are several difficulties in applying such methods. For instance, it is now known from photoionization studies that ionization processes may be dominated by autoionization. Therefore, the onset of a new excited state is not necessarily characterized by an increased slope in the electron-impact ionization-efficiency curve, which is proportional to the probability of producing that state, as had been assumed earlier. Another problem arises because of the different radiative lifetimes that are characteristic of various excited ionic states (see Section I.A.4). 

Complexes of the form (CO)5MEPh3 (Table 5) are characterized by sufficiently high stability under electron impact ionization to form molecular ions of intermediate abundance . Their decomposition involves consecutive decarbonylation forming M(CO) EPh3" ions (n = 0-4). Cleavage of the M—E bond is observed only in PhjEM" with both M and EPhj" " ions being produced. 

Xylenes in drinking water, wastewaters, soils, and hazardous wastes may be analyzed by EPA analytical procedures (Methods 501, 602, 524, 624, 1624, 8020, and 8240) (U.S. EPA 1992 1997). These methods involve concentration of the analytes by purging and trapping over suitable adsorbent columns before their GC or GC/MS analyses. The primary characteristic ion for GC/MS identification (by electron-impact ionization) is 106, which characterizes ethylbenzene as well. Photoionization and flame ionization detectors are, in general, suitable for ppb- andppm-level GC analysis, respectively. Air analysis may be done by NIOSH Method 1501 (see Section 26.2). 

In response to this need, aerosol mass spectrometry has developed rapidly and it is now possible to determine both the size (over a limited size range) and qualitative chemical composition of most gas-phase aerosols, with a response time of less than 1 s (see Suess and Prather (1999)). Most of the instruments described in the literature use laser ablation and ionization of the aerosol particles to characterize their chemical composition, but other methods, including thermal vaporization with electron impact ionization, are also used. Here, we first briefly sketch the development of instruments based on laser ablation/ ionization techniques and then describe some of the work that has been done using an aerosol TOP mass spectrometer. 

Mass spectroscopy is a useful technique for the characterization of dendrimers because it can be used to determine relative molar mass. Also, from the fragmentation pattern, the details of the monomer assembly in the branches can be confirmed. A variety of mass spectroscopic techniques have been used for this, including electron impact, fast atom bombardment and matrix-assisted laser desorption ionization (MALDI) mass spectroscopy. 

Due to the high mass, low volatility, and thermal instability of chlorophylls and derivatives, molecular weight determination by electron impact (El) MS is not recommended. Desorption-ionization MS techniques such as chemical ionization, secondary ion MS, fast-atom bombardment (FAB), field, plasma- and matrix-assisted laser desorption have been very effective for molecular ion detection in the characterization of tetrapyrroles. These techniques do not require sample vaporization prior to ionization and they are effective tools for allomerization studies. 

Mass spectrometry (MS) in its various forms, and with various procedures for vaporization and ionization, contributes to the identification and characterization of complex species by their isotopomer pattern of the intact ions (usually cation) and by their fragmentation pattern. Upon ionization by the rough electron impact (El) the molecular peak often does not appear, in contrast to the more gentle field desorption (FD) or fast-atom bombardment (FAB) techniques. An even more gentle way is provided by the electrospray (ES) method, which allows all ionic species (optionally cationic or anionic) present in solution to be detected. Descriptions of ESMS and its application to selected problems are published 45-47 also a representative application of this method in a study of phosphine-mercury complexes in solution is reported.48... 

With the surface ionization source it is generally assumed that the reactant ion internal state distribution is characterized by the source temperature and that the majority of the reactant ions are in their ground electronic state. This contrasts with the uncertainty in reactant state distributions when transition metal ions are generated by electron impact fragmentation of volatile organometallic precursors (10) or by laser evaporation and ionization of solid metal targets (11). Many examples... 

Photoionization, as already pointed out, is characterized by a step function for ionization probabiUty versus energy. The change in mode of ionization is thus much more easily detectable than for electron impact which produces only changes of slope. The combination of photon impact ion sources with mass analysis has been a major advance in technique since it has allowed the direct study of formation and breakdown of excited ions. The first account of such an experiment was given by Hurzeler, Inghram and Morrison (1958) who employed the especially convenient Seya-Namioka type of monochromator, which had then just been described, in conjunction with a conventional magnetic sector mass... 

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). 

A striking feature of the ILs is their low vapor pressure. This, on the other hand, is a factor hampering their investigation by MS. For example, a technique like electron impact (El) MS, based on thermal evaporation of the sample prior to ionization of the vaporized analyte by collision with an electron beam, has only rarely been applied for the analysis of this class of compounds. In contrast, nonthermal ionization methods, like fast atom bombardment (FAB), secondary ion mass spectrometry (SIMS), atmospheric pressure chemical ionization (APCI), ESI, and MALDI suit better for this purpose. Measurement on the atomic level after burning the sample in a hot plasma (up to 8000°C), as realized in inductively coupled plasma (ICP) MS, has up to now only rarely been applied in the field of IE (characterization of gold particles dissolved in IE [1]). This method will potentially attract more interest in the future, especially, when the coupling of this method with chromatographic separations becomes a routine method. 

Utilizing ionization efficiency curves to determine relative populations of vibrationally excited states (as in the photoionization experiments) is a quite valid procedure in view of the long radiative lifetime that characterizes vibrational transitions within an electronic state (several milliseconds). However, use of any ionization efficiency curve (electron impact, photon impact, or photoelectron spectroscopic) to obtain relative populations of electronically excited states requires great care. A more direct experimental determination using a procedure such as the attenuation method is to be preferred. If the latter is not feasible, accurate knowledge of the lifetimes of the states is necessary for calculation of the fraction that has decayed within the time scale of the experiment. Accurate Franck -Condon factors for the transitions from these radiating states to the various lower vibronic states are also required for calculation of the modified distribution of internal states relevant to the experiment.991 102... 

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