Molecule ions

At the limit of extremely low particle densities, for example under the conditions prevalent in interstellar space, ion-molecule reactions become important (see chapter A3.51. At very high pressures gas-phase kinetics approach the limit of condensed phase kinetics where elementary reactions are less clearly defined due to the large number of particles involved (see chapter A3.6). 

LIF has been used to study state-selected ion-atom and ion-molecule collisions in gas cells. Ar reactions with N2 and CO were investigated by Leone and colleagnes in the 1980s [13, 14] and that group has... 

The decrease in reactivity with increasing temperature is due to the fact that many low-energy ion-molecule reactions proceed tln-ough a double-well potential with the following mechanism [82] ... 

Another powerftil class of instmnientation used to study ion-molecule reactivity is trapping devices. Traps use electric and magnetic fields to store ions for an appreciable length of time, ranging from milliseconds to thousands of seconds. Generally, these devices mn at low pressure and thus can be used to obtain data at pressures well below the range in which flow tubes operate. 

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... 

As with most methods for studying ion-molecule kinetics and dynamics, numerous variations exist. For low-energy processes, the collision cell can be replaced with a molecular beam perpendicular to the ion beam [106]. This greatly reduces the thennal energy spread of the reactant neutral. Another approach for low energies is to use a merged beam [103]. In this system the supersonic expansion is aimed at the tluoat of the octopole, and the ions are passed tluough... 

Several instniments have been developed for measuring kinetics at temperatures below that of liquid nitrogen [81]. Liquid helium cooled drift tubes and ion traps have been employed, but this apparatus is of limited use since most gases freeze at temperatures below about 80 K. Molecules can be maintained in the gas phase at low temperatures in a free jet expansion. The CRESU apparatus (acronym for the French translation of reaction kinetics at supersonic conditions) uses a Laval nozzle expansion to obtain temperatures of 8-160 K. The merged ion beam and molecular beam apparatus are described above. These teclmiques have provided important infonnation on reactions pertinent to interstellar-cloud chemistry as well as the temperature dependence of reactions in a regime not otherwise accessible. In particular, infonnation on ion-molecule collision rates as a ftmction of temperature has proven valuable m refining theoretical calculations. 

Most ion-molecule techniques study reactivity at pressures below 1000 Pa however, several techniques now exist for studying reactions above this pressure range. These include time-resolved, atmospheric-pressure, mass spectrometry optical spectroscopy in a pulsed discharge ion-mobility spectrometry [108] and the turbulent flow reactor [109]. 

Although this reaction is exothemiic, the reaction has a small rate constant. This is one of the most studied ion-molecule reactions, and dependences on many parameters have been measured [148]. 

Franklin J L (ed) 1979 Ion-Molecule Reactions, Part I, Kinetics and Dynamics (Stroudsburg, PA Dowden, Hutchinson and Ross)... 

Troe J 1992 Statisticai aspects of ion-moiecuie reactions State-Selected and State-to-State Ion-Molecule Reaction Dynamics Theory ed M Baer M and C-Y Ng (New York Wiiey)... 

Ikezoe Y, Matsuoka S, Takebe M and Viggiano A A 1987 Gas Phase Ion-Molecule Reaction Rate Constants Through 1986 (Tokyo Maruzen)... 

Smith M A 1994 Ion-molecule reaction dynamics at very low temperatures Unimolecular and Bimolecular Ion-Molecule Reaction Dynamics ed C-Y Ng, T Baer and I Powis (New York Wiley)... 

Viggiano A A and Morris R A 1996 Rotational and vibrational energy effects on ion-molecule reactivity as studied by the VT-SIFDT technique J. Phys. Chem. 100 19 227-40... 

Ferguson E E 1992 A personal history of the early development of the flowing afterglow technique for ion molecule reactions studies J. Am. Soc. Mass Spectrom. 3 479-86... 

Adams N G and Smith D 1988 Flowing afterglow and SIFT Techniques for the Study of Ion-Molecule Reactions ed J M Farrar and W FI Saunders Jr (New York Wiley)... 

Flierl P M ef a/1996 Flowing afterglow apparatus for the study of ion-molecule reactions at high temperatures Rev. Scl. Instrum. 67 2142-8... 

McFarland M, Albritton D L, Fehsenfeld F C, Ferguson E E and Schmeltekopf A L 1973 Flow-drift technique for ion mobility and ion-molecule reaction rate constant measurements. I. Apparatus and mobility measurements J. Chem. Phys. 59 6610-19... 

Ferguson E E 1979 ion-moiecuie reactions in the atmosphere K/nef/cs of Ion-Molecule Reactions ed P Ausioos (New York Pienum)... 

Tlie best place to start for a detailed look at the instrumentation for the study of ion-molecule chemistry. 

A comprehensive look at the effect of state selection on ion-molecule reactions from both experimental and theoretical viewpoints. 

Collision-induced dissociation mass spectrum of tire proton-bound dimer of isopropanol [(CH2)2CHOH]2H. The mJz 121 ions were first isolated in the trap, followed by resonant excitation of their trajectories to produce CID. Fragment ions include water loss mJz 103), loss of isopropanol mJz 61) and loss of 42 anui mJz 79). (b) Ion-molecule reactions in an ion trap. In this example the mJz 103 ion was first isolated and then resonantly excited in the trap. Endothennic reaction with water inside the trap produces the proton-bound cluster at mJz 121, while CID produces the fragment with mJz 61. 

The same procedure as outlined above can be used to study ion-molecule reactions [15, 34]- Mass-selected ions will react with neutral species inside the trap. The presence of the damping gas means that stable (tliemiodynamic and... 

Time-of-flight mass spectrometers have been used as detectors in a wider variety of experiments tlian any other mass spectrometer. This is especially true of spectroscopic applications, many of which are discussed in this encyclopedia. Unlike the other instruments described in this chapter, the TOP mass spectrometer is usually used for one purpose, to acquire the mass spectrum of a compound. They caimot generally be used for the kinds of ion-molecule chemistry discussed in this chapter, or structural characterization experiments such as collision-induced dissociation. Plowever, they are easily used as detectors for spectroscopic applications such as multi-photoionization (for the spectroscopy of molecular excited states) [38], zero kinetic energy electron spectroscopy [39] (ZEKE, for the precise measurement of ionization energies) and comcidence measurements (such as photoelectron-photoion coincidence spectroscopy [40] for the measurement of ion fragmentation breakdown diagrams). 

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... 

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