Cyclotron resonance

This technique provides quantitative information about tautomeric equilibria in the gas phase. The results are often complementary to those obtained by mass spectrometry (Section VII,E). In principle, gas-phase proton affinities, as determined by ICR, should provide quantitative data on tautomeric equilibria. The problem is the need to correct the measured values for the model compounds, generally methyl derivatives, by the so-called N-, 0-, or S-methylation effect. Since the difference in stability between tautomers is generally not too large (otherwise determination of the most stable tautomer is trivial) and since the methylation effects are difficult to calculate, the result is that proton affinity measurements allow only semi-quantitative estimates of individual tautomer stabilities. This is a problem similar to but more severe than that encountered in the method using solution basicities (76AHCS1, p. 20). 

Katritzky and Taft were the first to use ICR proton affinities for tautomeric studies (76JA6048). This and work of Katritzky and Nibbering (77TL1777) discuss the tautomerism of pyridones and thiopyridones and conclude that ICR results are in agreement with previous studies of Beak (76JA171)—that in the gas phase the OH and SH tautomers predominate. The complicated case of 2-thiouracil (six aromatic tautomers) was studied by Katritzky and Eyler [89JCS(P2)1499] they conclude that the oxothioxo tautomer is the most stable. 

In the field of azoles, Catalan, Abboud, and Elguero [87AHC(41)187] carried out a series of studies which show the interest of the ICR method for a case where the correction always corresponds to an N-methylation effect which can be estimated accurately. This is the case for (1) the annular tautomerism of indazole and its relationship with the annulation effect 

The effective masses of electrons and holes can be measrued by irradiating the material with circularly polarized radio frequency (microwave) radiation in the presence of a magnetic field. The equation of motion is 

Let the magnetic field be in the z-direction and the right-hand circularly polarized radiation be given by Ex = Eoe and Ey = —iEge K The solution to Equation 19.22 can be written as and Vy = —ivoe . Inserting these quantities into Equation 19.22 and identifying the cyclotron frequency as tOc = cBzjm, the Vq can be written as 

The resonant or cyclotron frequency is detected by absorption of power from the micro-wave beam which becomes a maximum when o = 0c, as can be seen from Equation 19.26. The effective electron mass can then be determined from m = eB z/ c- The effective mass of holes can be found in a similar manner using left-hand polarized microwave radiation. 

In conductive metals, it is difficult to penetrate to much depth with microwave radiation. The magnetic field and the microwave beam are oriented along the surface of the conductor. The circulating electrons will only feel the field when they are within the skin depth of the radiation, so when the applied frequency is some integer times the resonance frequency, absorption will occur. This technique is known as the Azbel-Kramer cyclotron resonance (AKCR) method. 

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The most widely used type of trap for the study of ion-molecule reactivity is the ion-cyclotron-resonance (ICR) [99] mass spectrometer and its successor, the Fourier-transfomi mass spectrometer (FTMS) [100, 101]. Figure A3.5.8 shows the cubic trapping cell used in many FTMS instmments [101]. Ions are created in or injected into a cubic cell in a vacuum of 10 Pa or lower. A magnetic field, B, confines the motion in the x-y... 

The chapter is divided into sections, one for each general class of mass spectrometer magnetic sector, quadnipole, time-of-flight and ion cyclotron resonance. The experiments perfonned by each are quite often unique and so have been discussed separately under each heading. 

B1.7.6 FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETERS... 

Figure Bl.7.18. (a) Schematic diagram of the trapping cell in an ion cyclotron resonance mass spectrometer excitation plates (E) detector plates (D) trapping plates (T). (b) The magnetron motion due to tire crossing of the magnetic and electric trapping fields is superimposed on the circular cyclotron motion aj taken up by the ions in the magnetic field. Excitation of the cyclotron frequency results in an image current being detected by the detector electrodes which can be Fourier transfonned into a secular frequency related to the m/z ratio of the trapped ion(s).

Mclver R T 1970 A trapped ion analyzer cell for ion cyclotron resonance spectroscopy Rev. Sc/. Instrum. 41 555-8... 

Vartanian V H, Anderson J S and Laude D A 1995 Advances in trapped ion cells for Fourier transform ion cyclotron resonance mass spectrometry Mass Spec. Rev. 41 1-19... 

Comisarow M B and Marshall A G 1996 Early development of Fourier transform ion cyclotron resonance (FT-ICR) spectroscopy J. Mass Spectrom. 31 581-5... 

Grover R, Decouzon M, Maria P-C and Gal J-F 1996 Reliability of Fourier transform-ion cyclotron resonance determinations of rate constants for ion/molecule reactions Eur. Mass Spectrom. 2 213-23... 

Fisher J J and McMahon T B 1990 Determination of rate constants for low pressure association reactions by Fourier transform-ion cyclotron resonance Int. J. Mass Spectrom. Ion. Proc 100 707-17... 

The reactivity of size-selected transition-metal cluster ions has been studied witli various types of mass spectrometric teclmiques [1 ]. Fourier-transfonn ion cyclotron resonance (FT-ICR) is a particularly powerful teclmique in which a cluster ion can be stored and cooled before experimentation. Thus, multiple reaction steps can be followed in FT-ICR, in addition to its high sensitivity and mass resolution. Many chemical reaction studies of transition-metal clusters witli simple reactants and hydrocarbons have been carried out using FT-ICR [49, 58]. 

Microwave discharges at pressures below 1 Pa witli low collision frequencies can be generated in tlie presence of a magnetic field B where tlie electrons rotate witli tlie electron cyclotron frequency. In a magnetic field of 875 G tlie rotational motion of tlie electrons is in resonance witli tlie microwaves of 2.45 GHz. In such low-pressure electron cyclotron resonance plasma sources collisions between tlie atoms, molecules and ions are reduced and the fonnation of unwanted particles in tlie plasma volume ( dusty plasma ) is largely avoided. 

Other types of mass spectrometer may use point, array, or both types of collector. The time-of-flight (TOF) instrument uses a special multichannel plate collector an ion trap can record ion arrivals either sequentially in time or all at once a Fourier-transform ion cyclotron resonance (FTICR) instrument can record ion arrivals in either time or frequency domains which are interconvertible (by the Fourier-transform technique). 

Other types of mass spectrometer can use point, array, or both types of ion detection. Ion trap mass spectrometers can detect ions sequentially or simultaneously and in some cases, as with ion cyclotron resonance (ICR), may not use a formal electron multiplier type of ion collector at all the ions can be detected by their different electric field frequencies in flight. 

Commercial mass analyzers are based almost entirely on quadrupoles, magnetic sectors (with or without an added electric sector for high-resolution work), and time-of-flight (TOE) configurations or a combination of these. There are also ion traps and ion cyclotron resonance instruments. These are discussed as single use and combined (hybrid) use. 

An added consideration is that the TOF instruments are easily and quickly calibrated. As the mass range increases again (m/z 5,000-50,000), magnetic-sector instruments (with added electric sector) and ion cyclotron resonance instruments are very effective, but their prices tend to match the increases in resolving powers. At the top end of these ranges, masses of several million have been analyzed by using Fourier-transform ion cyclotron resonance (FTICR) instruments, but such measurements tend to be isolated rather than targets that can be achieved in everyday use. 

A simple mass spectrometer of low resolution (many quadrupoles, magnetic sectors, time-of-flight) cannot easily be used for accurate mass measurement and, usually, a double-focusing magnetic/electric-sector or Fourier-transform ion cyclotron resonance instrument is needed. 

Ion cyclotron resonance analyzer. A device to determine the mass-to-charge ratio (m/z) of an ion in the presence of a magnetic field by measuring its cyclotron frequency. 

Mass spectrometer configuration. Multianalyzer instruments should be named for the analyzers in the sequence in which they are traversed by the ion beam, where B is a magnetic analyzer, E is an electrostatic analyzer, Q is a quadrupole analyzer, TOP is a time-of-flight analyzer, and ICR is an ion cyclotron resonance analyzer. For example BE mass spectrometer (reversed-geometry double-focusing instrument), BQ mass spectrometer (hybrid sector and quadrupole instrument), EBQ (double-focusing instrument followed by a quadrupole). 

FTICR. Fourier-transform ion cyclotron resonance GC/IRMS. gas chromatography isotope ratio mass spectrometry... 

ICP/MS. inductively coupled plasma and mass spectrometry used as a combined technique ICR. ion cyclotron resonance (spectroscopy)... 

Asamoto, B. and Dunbar, R.C., Analytical Applications of Fourier Transform Ion Cyclotron Resonance Spectroscopy, VCH, New York, 1991. 

Lehman, T.A. and Bursey, M.M., Ion Cyclotron Resonance Spectroscopy, Wiley, New York, 1976. 

The result of the Back-to-Basics series is an accumulation of some 50 separate but interrelated expositions of mass spectrometric principles and apparatus. Some areas of mass spectrometry, such as ion cyclotron resonance and ion trap instruments, have not been covered except for passing references. This decision has not been due to any bias by the authors or Micromass but simply reflects the large amount of writing that had to be done and the needs of the greatest proportion of users. 

A particularly useful property of the PX monomer is its enthalpy of formation. Conventional means of obtaining this value, such as through its heat of combustion, are, of course, excluded by its reactivity. An experimental attempt was made to obtain this measure of chemical reactivity with the help of ion cyclotron resonance a value of 209 17 kJ/mol (50 4 kcal/mol) was obtained (10). Unfortunately, the technique suffers from lack of resolution in addition to experimental imprecision. It is perhaps better to rely on molecular orbital calculations for the formation enthalpy. Using a semiempirical molecular orbital technique, which is tuned to give good values for heat of formation on experimentally accessible compounds, the heat of formation of /5-xylylene has been computed to be 234.8 kj/mol (56.1 kcal/mol) (11). 

The requirements of thin-film ferroelectrics are stoichiometry, phase formation, crystallization, and microstmctural development for the various device appHcations. As of this writing multimagnetron sputtering (MMS) (56), multiion beam-reactive sputter (MIBERS) deposition (57), uv-excimer laser ablation (58), and electron cyclotron resonance (ECR) plasma-assisted growth (59) are the latest ferroelectric thin-film growth processes to satisfy the requirements. 

The existence of the XeCHg [34176-86-8] cation has been estabtished ia the gas phase. The Xe—C bond energy of the XeCHg cation has been estimated to be 180 A 33 kJ/mol (112) and more recently, 231 A 10 kJ/mol (113) by ion cyclotron resonance. The compound Xe(CF3)2 [72599-34-9] is reported to be a waxy white sotid having a half-life of ca 30 min at room temperature (114). The synthesis iavolved the addition of XeF2 to a tritiuoromethyl plasma, but the characterization of this compound is limited and has not been iadependently confirmed. 

The most common modes of operation for ms/ms systems include daughter scan, parent ion scan, neutral loss scan, and selected reaction monitoring. The mode chosen depends on the information required. Stmctural identification is generally obtained using daughter or parent ion scan. The mass analyzers commonly used in tandem systems include quadmpole, magnetic-sector, electric-sector, time-of-flight, and ion cyclotron resonance. Some instmments add a third analyzer such as the triple quadmpole ms (27). 

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