Field ionization method

The advent of tunable lasers created a radically new situation as to the possibility for selective excitation of high Rydberg states and for making precise measurements on their properties. Highly excited atoms are very sensitive to external fields, and currently used field ionization methods are very powerful for detecting Rydberg states. As a consequence of these circumstances, such an old problem as the Stark effect in atomic hydrogen attracted a renewed interest. 

The Rydberg atom experiments described above are well adapted to the study of the atomic observables via the very sensitive field ionization method. The observation of the field itself and its fluctuations would also be very interesting. (In the Bloch vector model, the field variables are associated to the pendulum velocity whereas the atomic ones are related to its position). It has recently been shown either by full quantum mechanical calculations or by the Bloch vector semi-classical approach that if the system is initially triggered by a small external field impinging on the cavity, the fluctuations on one phase of the field become at some time smaller than in the vacuum field. This is a case of radiation "squeezing" which would be very interesting to study on Rydberg atom maser systems. 

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 ). 

A major advantage of the TOF mass spectrometer is its fast response time and its applicability to ionization methods that produce ions in pulses. As discussed earlier, because all ions follow the same path, all ions need to leave the ion source at the same time if there is to be no overlap between m/z values at the detector. In turn, if ions are produced continuously as in a typical electron ionization source, then samples of these ions must be utihzed in pulses by switching the ion extraction field on and off very quickly (Figure 26.4). 

The study of metastable ions concerns substances that have been ionized by electrons and have undergone fragmentation. The stable molecular ions that are formed by soft ionization methods (chemical ionization. Cl field ionization, FI) need a boost of extra energy to make them fragment, but in such cases other methods of investigation than linked scanning are generally used. 

Anbar, Determination of Subprogram Amounts of Chemical Agents in the Atmosphere , Edge-woodArs Contract Rept EC-CR-74028, SRI Proj 3122 (1974) ( A method of mass spectroscopy, employing a silicone membrane and field ionization, which involves other new techniques, is presented which is sensitive to picogram amts of chemical agents in the atm)... 

Various ionization methods were used to bombard phenol-formaldehyde oligomers in mass spectroscopic analysis. The molecular weights of resole resins were calculated using field desorption mass spectroscopy of acetyl-derivatized samples.74 Phenol acetylation was used to enable quantitative characterization of all molecular fractions by increasing the molecular weights in increments of 42. 

A more constructive approach to nuclear fusion—one that achieves a controlled release of nuclear energy—is to heat a plasma, or ionized gas, by passing an electric current through it. The very fast ions in the plasma are kept away from the walls of the container with magnetic fields. This method of achieving fusion is the subject of intense research and is beginning to show signs of success (Fig. 17.27). 

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). 

Field desorption An ionization method in which sample is deposited on a wire to which a high voltage is applied. 

The term electrospray reveals important features of the process first of all, and differently from the ionization methods described so far, the ionization occurs on a spray. This is produced by forcing a liquid to pass through a capillary, as occurs with perfume dispensers. This causes the formation of millions and millions of small droplets. The first part of the ionization s term contains further important information an electric field (3 5 kV) is applied to the capillary and it causes ionization (Figure 2.3). The overall effect is the formation of small liquid-charged droplets from which gas phase ions are formed. ESI is governed by a large number of chemical and physical parameters that... 

Volatile or volatilizable compounds may be introduced into the spectrometer via a pinhole aperture or molecular leak which allows a steady stream of sample molecules into the ionization area. Non-volatile or thermally labile samples are introduced directly by means of an electrically heated probe inserted through a vacuum lock. Numerous methods of sample ionization are available of which the most important are electron impact (El), chemical ionization (CY), field ionization (FI), field desorption (FD), fast atom bombardment (FAB), and radio-frequency spark discharge. 

Field desorption (FD) was introduced by Beckey in 1969 [76]. FD was the first soft ionization method that could generate intact ions from nonvolatile compounds, such as small peptides [77]. The principal difference between FD and FI is the sample injection. Rather than being in the gas phase as in FI, analytes in FD are placed onto the emitter and desorbed from its surface. Application of the analyte onto the emitter can be performed by just dipping the activated emitter in a solution. The emitter is then introduced into the ion source of the spectrometer. The positioning of the emitter is cmcial for a successful experiment, and so is the temperature setting. In general, FI and FD are now replaced by more efficient ionization methods, such as MALDI and ESI. For a description of FD (and FI), see Reference 78. 

Stereochemical aspects in mass spectrometry have aroused more and more interest. El mass spectra of stereoisomers are practically indistinguishable. However, the use of soft ionization methods (chemical ionization, field ionization, etc.) accompanied by tandem mass spectrometry allows important and reliable conclusions on the molecular structures to be drawn. 

The quadrupole ion trap (QIT) creates a three-dimensional RF quadrupole field to store ions within defined boundaries. Its invention goes back to 1953, [103-105] however, it took until the mid-1980s to access the full analytical potential of quad-mpole ion traps. [137-140] The first commercial quadmpole ion traps were incorporated in GC-MS benchtop instruments (Finnigan MAT ITD and ITMS). Electron ionization was effected inside the trap by admitting the GC effluent and a beam of electrons directly into the storage volume of the trap. Later, external ion sources became available, and soon a large number of ionization methods could be... 

With external ion sources it became feasible to interface any ionization method to the QIT mass analyzer. [171] However, commercial QITs are chiefly offered for two fields of applications i) GC-MS systems with El and Cl, because they are either inexpensive or capable of MS/MS to improve selectivity of the analysis (Chap. 12) and ii) instruments equipped with atmospheric pressure ionization (API) methods (Chap. 11) offering higher mass range, and some 5-fold unit resolution to resolve isotopic patterns of multiply charged ions (Fig. 4.47). [149,162,172,173]... 

The localization of a double bond is an important step in structure elucidation and therefore, it is not astonishing that numerous approaches have been made to overcome the above limitations. The methods to freeze isomerization include i) epoxidation [64], ii) iron and copper ion chemical ionization [65,66], iii) field ionization [67], iv) collision-induced dissociation [60], v) formation of thioether derivatives, [68,69] and others. 

Very large branched alkanes, such as 24,24-diethyl-19,29-dioctadecylhepta-tetracontane, CgvHng, for example, pose difficulties to obtaining useful mass spectra and even 15 eV El does not anymore allow for the detection of their molecular ions. [80] Beyond C40 alkanes, especially in case of mixtures such as hydrocarbon waxes or polyethylenes of low molecular weight, field desorption and matrix-assisted laser desorption/ionization are the ionization methods of choice (Chaps. 8, 10). 

---