Electron and ion spectrometry

The quantitative evaluation of relative intensities for selected photo- or Auger processes requires information about both the relative kinetic energy dependence of the analyser transmission T (see Fig. 4.15) and the accompanying detection efficiency e of the electron detector. The relative magnitude for the desired product Te can be determined directly if, for example, non-coincident electron and ion spectrometry are combined with helium as target gas, the Is photoline is recorded as a function of the photon energy and yields the dispersion corrected area AD (electron) see equ. (2.39) ... 

The positive column is a region in which atoms, electrons, and ions are all present together in similar numbers, and it is referred to as a plasma. Again, as with the corona discharge, in mass spectrometry, plasmas are usually operated in gases at or near atmospheric pressure. 

Passivation of active metals to hydrogen reaction has been recognized as an important problem in basic metal-hydrogen studies, especially in their technological application to various situations. Few investigations have addressed these difficulties. The advent of modern surface analytical techniques such as photoelectron spectroscopyy Auger electron spectroscopy, and ion spectrometry offer a tremendous opportunity to attack the passivation question. Each of these techniques is discussed with regard to their capabilities and application to hydride kinetics. 

If a sample solution is introduced into the center of the plasma, the constituent molecules are bombarded by the energetic atoms, ions, electrons, and even photons from the plasma itself. Under these vigorous conditions, sample molecules are both ionized and fragmented repeatedly until only their constituent elemental atoms or ions survive. The ions are drawn off into a mass analyzer for measurement of abundances and mJz values. Plasma torches provide a powerful method for introducing and ionizing a wide range of sample types into a mass spectrometer (inductively coupled plasma mass spectrometry, ICP/MS). 

An AutoSpec-TOF mass spectrometer has a magnetic sector and an electron multiplier ion detector for carrying out one type of mass spectrometry plus a TOF analyzer with a microchannel plate multipoint ion collector for another type of mass spectrometry. Either analyzer can be used separately, or the two can be run in tandem (Figure 20.4). 

Some of the target molecules gain so much excess internal energy in a short space of time that they lose an electron and become ions. These are the molecular cation-radicals found in mass spectrometry by the direct absorption of radiation. However, these initial ions may react with accompanying neutral molecules, as in chemical ionization, to produce protonated molecules. 

Electron impact mass spectrometry has been employed to study the fragmentation patterns of isoxazolylmethyl- and bis(isoxazolylmethyl)-isoxazoles and the results are in agreement with proposed pathways (79AC(R)8l). Electron impact studies of nitrostyryl isoxazole (6) show fragmentation in a variety of ways. The standard loss of NO2 from the molecular ion... 

Diphenylthiirene 1-oxide and several thiirene 1,1-dioxides show very weak molecular ions by electron impact mass spectrometry, but the molecular ions are much more abundant in chemical ionization mass spectrometry (75JHC21). The major fragmentation pathway is loss of sulfur monoxide or sulfur dioxide to give the alkynic ion. High resolution mass measurements identified minor fragment ions from 2,3-diphenylthiirene 1-oxide at mje 105 and 121 as PhCO" and PhCS, which are probably derived via rearrangement of the thiirene sulfoxide to monothiobenzil (Scheme 2). 

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