Quadmpole

In many respects, the applications of FT-ICR are similar to those of the quadmpole ion trap, as they are both trapping instmments. The major difference is in the ion motion inside the trapping cell and the wavefomi detection. In recent... 

As with the quadmpole ion trap, ions with a particular m/z ratio can be selected and stored in tlie FT-ICR cell by the resonant ejection of all other ions. Once isolated, the ions can be stored for variable periods of time (even hours) and allowed to react with neutral reagents that are introduced into the trapping cell. In this maimer, the products of bi-molecular reactions can be monitored and, if done as a fiinction of trapping time, it is possible to derive rate constants for the reactions [47]. Collision-induced dissociation can also be perfomied in the FT-ICR cell by tlie isolation and subsequent excitation of the cyclotron frequency of the ions. The extra translational kinetic energy of the ion packet results in energetic collisions between the ions and background... 

There are otlier teclmiques for mass separation such as tire quadmpole mass filter and Wien filter. Anotlier mass spectrometry teclmique is based on ion chromatography, which is also capable of measuring tire shapes of clusters [30, 31]. In tills metliod, cluster ions of a given mass are injected into a drift tube witli well-defined entrance and exit slits and filled witli an inert gas. The clusters drift tlirough tills tube under a weak electric potential. Since the... 

There are other important properties tliat can be measured from microwave and radiofrequency spectra of complexes. In particular, tire dipole moments and nuclear quadmpole coupling constants of complexes may contain useful infonnation on tire stmcture or potential energy surface. This is most easily seen in tire case of tire dipole moment. The dipole moment of tire complex is a vector, which may have components along all tire principal inertial axes. 

Note that Equation 25.1 shows that the field (F) has no effect along the direction of the central (z) axis of the quadmpole assembly, so, to make ions move in this direction, they must first be accelerated through a small electric potential (typically 5 V) between the ion source and the assembly. Because of the oscillatory nature of the field (F Figure 25.3), an ion trajectory as it moves through the quadmpole assembly is also oscillatory. 

Passage through the quadmpole assembly is described as stable motion, while those trajectories that lead ions to strike the poles is called unstable motion. From mathematical solutions to the equations of motion for the ions, based on Equation 25.1, two factors (a and q Equation 25.2) emerge as being important in defining regions of stable ion trajectory. 

For small values of a and q, the shaded area in Figure 25.4 indicates an area of stable ion motion it shows all values for a and q for which ions can be transmitted through the quadmpole assembly. 

To gain some idea of the meaning of this shaded area, consider the straight line OA of slope a/q shown in Figure 25.4. The line enters the region of stable motion at P and leaves it at Q. For typical values of U (1000 V), V (6000 V), co (1.5 MHz), and r (1.0 cm). Equation 25.2 predicts that point P corresponds to an ion of m/z 451 and Q to m/z 392. Therefore, with these parameter values, all ions having m/z between 392 and 451 will be transmitted through the quadmpole. 

Quadmpole mass spectrometers (mass filters) allow ions at each m/z value to pass through the analyzer sequentially. For example, ions at m/z 100, 101, and 102 are allowed to pass one after the other through the quadmpole assembly so that first m/z 100 is transmitted, then m/z 101, then m/z 102, and so on. Therefore, the ion collector at the end of the quadmpole unit needs to cover only one point or focus in space and can be placed immediately behind the analyzer (Figure 30.1). A complete mass spectram is recorded over a period of time (temporally), which is set by the voltages on the quadmpole analyzer. In this mode of operation, the ions are said to be scanned sequentially. The resolution of m/z values is dependent solely on the analyzer and not on the detector. The single-point collector is discussed in detail in Chapter 28. 

In a sector instrument, which acts as a combined mass/velocity filter, this difference in forward velocity is used to effect a separation of normal and metastable mj" ions (see Chapter 24, Ion Optics of Magnetic/Electric-Sector Mass Spectrometers ). However, as discussed above, the velocity difference is of no consequence to the quadmpole instrument, which acts only as a mass filter, so the normal and metastable mj ions formed in the first field-free region (Figure 33.1) are not differentiated. 

Magnetic/electrostatic analyzer-collision cell-quadmpole... 

Quadmpoles or hexapoles are used as transmission guides for both slow and fast ions. In both cases, the objective is to ensure that as many ions as possible are guided from the entrance of the device to its exit. The ions are usually in transit in a straight line between an ion source and a mass analyzer. Any ions within the transmission guides that are deflected from the desired trajectory are pushed or pulled back on course by the action of the inhomogeneous RF fields applied to the poles of the guides. 

This focusing action gives an ion beam, in which the m/z values can be measured so accurately that the resolution of a magnetic/electric-sector instrument (separation of ions of different m/z values) is measured as a few parts per million, compared to the more modest few parts per thousand in, say, a quadmpole or ion-trap instrument. 

This system is very similar to that of a hybrid quadmpole time-of-flight (Q/TOP) instrument but without the initial quadmpole section. 

A quadmpole analyzer can be operated in either RF mode only or in RF/DC mode. 

Rather than looking at just the low-abundance metastable ion processes occurring in the second quadrupole, extra fragmentation can be induced by having a neutral collision gas present in this quadmpole. 

If an ion has to travel from one end of a quadmpole to the other, it must have some kinetic energy in the z-direction. This kinetic energy can be induced by application of an accelerating potential to the ions before they enter the quadrupole field. 

Forces of Adsorption. Adsorption may be classified as chemisorption or physical adsorption, depending on the nature of the surface forces. In physical adsorption the forces are relatively weak, involving mainly van der Waals (induced dipole—induced dipole) interactions, supplemented in many cases by electrostatic contributions from field gradient—dipole or —quadmpole interactions. By contrast, in chemisorption there is significant electron transfer, equivalent to the formation of a chemical bond between the sorbate and the soHd surface. Such interactions are both stronger and more specific than the forces of physical adsorption and are obviously limited to monolayer coverage. The differences in the general features of physical and chemisorption systems (Table 1) can be understood on the basis of this difference in the nature of the surface forces. 

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