Field ionization process

Field ionization essentially is a process of the autoionization type, i.e., an internally supra-excited atom or molecular moiety loses an electron spontaneously without further interaction with an energy source. [32] Different from electron ionization, there is no excess energy transferred onto the incipient ion, and thus, dissociation of the ions is reduced to minimum. 

In practice, electric fields sufficient to effect field ionization are only obtained in close proximity to sharp tips, edges, or thin wires. The smaller the radius of the curvature of the anode, the further away (1-10 nm) the field suffices to cause ionization. The importance of sufficient electric field strength is reflected by the half- 

Note The field anode is usually referred to as field emitter, FI emitter, or FD emitter. The properties of the field emitter are of key importance for FI- and FD-MS. The electrode on the opposite side is called field cathode or simply counter electrode. 

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There are basically two kinds of experiments which can be used for studying the mechanisms of the field ionization process near a field ion emitter surface and also the field ion image formation process. They are the measurement of field ion current as functions of tip voltage, tip temperature, and other experimental parameters, and the measurement of the ion energy distribution. 

The field ionization process can be considered as the reverse of a cold emission process. In the former, the electrons were injected... 

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 ). 

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. 

It is particularly difficult to study charge transfer reactions by the usual internal ionization method since the secondary ions produced will always coincide with ions produced in primary ionization processes. Indeed these primary ions frequently constitute the major fraction of the total ion current, and the small intensity changes originating from charge transfer reactions are difficult to detect. For example, Field and Franklin (5) were unable to detect any charge transfer between Xe + and CH4 by the internal ionization method although such reactions have been observed using other techniques (3, 9,22). 

Accelerated electrons in the applied electric field ionize gas molecules, and in these ionization processes extra electrons are created. In the steady state the loss of charged particles is balanced by their production. Due to their much lower mass, electrons move much faster than ions. As a result, charge separation creates... 

Under field ionization kinetic conditions (FIK) the process of CH3 elimination from ionized 27 is not observed at t < 10-10 sec. This is a surprising result bearing in... 

The narrowest PFI bands in the present study are 3 cm-1 FWHM, using a 0.5 V/cm extraction field with the lasers attenuated to minimize effects of space charge. We measure band positions at the intensity maxima. These are reproducible to better than 1 cm-1. The bandwidth is limited by the rotational contour and also by the ionization process. A major advantage of ZEKE-PFI over more traditional photoelectron techniques is that the energy calibration is that of the tunable dye lasers, which are quite stable from day to day. In contrast, both electrostatic analyzers and time-of-flight photoelectron spectrometers require frequent calibration. 

Gas-phase ion chemistry is a broad field which has many applications and which encompasses various branches of chemistry and physics. An application that draws together many of these branches is the synthesis of molecules in interstellar clouds (Herbst). This was part of the motivation for studies on the neutralization of ions by electrons (Johnsen and Mitchell) and on isomerization in ion-neutral associations (Adams and Fisher). The results of investigations of particular aspects of ion dynamics are presented in these association studies, in studies of the intermediates of binary ion-molecule Sn2 reactions (Hase, Wang, and Peslherbe), and in those of excited states of ions and their associated neutrals (Richard, Lu, Walker, and Weisshaar). Solvation in ion-molecule reactions is discussed (Castleman) and extended to include multiply charged ions by the application of electrospray techniques (Klassen, Ho, Blades, and Kebarle). These studies also provide a wealth of information on reaction thermodynamics which is critical in determining reaction spontaneity and availability of reaction channels. More focused studies relating to the ionization process and its nature are presented in the final chapter (Harland and Vallance). 

Scavenging experiments in hydrocarbon liquids (Rzad et al, 1970 Kimura and Fueki, 1970) tend to give low observed ionization yield, although the primary yield may be greater. The situation is similar for free-ion yield measurement under a relatively large external field. Both processes require large extrapolations to obtain the W value. 

Field desorption (FD) is similar in principle to FI. It enables ions to be produced directly from solid samples which are deposited from solution onto an anode fitted to a probe that can be inserted into the instrument via a vacuum lock. It is even more gentle than Cl and FI, producing molecular ions and virtually no fragmentation. However, the ionization process decays very rapidly so spectra must be scanned quickly and cannot be re-recorded without introducing more sample. 

Example Secondary kinetic isotope effects on the a-cleavage of tertiary amine molecular ions occurred after deuterium labeling both adjacent to and remote from the bond cleaved (Chap. 6.2.5). They reduced the fragmentation rate relative to the nonlabeled chain by factors of 1.08-1.30 per D in case of metastable ion decompositions (Fig. 2.18), but the isotope effect vanished for ion source processes. [78] With the aid of field ionization kinetic measurements the reversal of these kinetic isotope effects for short-lived ions (lO -lO" s) could be demonstrated, i.e., then the deuterated species decomposed slightly faster than their nonlabeled isoto-pomers (Fig. 2.17). [66,76]... 

In field ionization (as an experimental configuration) field ionization (the process) is the major pathway of ion generation. In field desorption from activated emitters, the analyte may also undergo field ionization. Presuming that the molecules are deposited in layers on the shanks of the whiskers or between them, this requires that i) analytes of low polarity are polarized by action of the electric field, ii) become mobile upon heating, and iii) finally reach the locations of ionizing electric... 

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