Modulation spectrometers

Figure 4.2 shows the complete CBMS II system. The main unit is comprised of three modules, the Biosampler Module, the Sample Introduction Module (SIM), and the Mass Spectrometer Module. The Biosampler Module houses the virtual impactor air particle concentrator and is only needed for the biological agent monitoring mode. The Sample Introduction Module contains the multiport sampling valve with its three input connections ... 

The Mass Spectrometer Module houses the vacuum system, capillary interface assembly, and ion-trap mass spectrometer in approximately half of the module. Also included are the reagent gas and calibration gas subassembly (a temperature-controlled housing that ensures consistent gas pressures). The other half contains the electronic printed circuit boards, power supplies, and instrument control computer. 

There are two alternatives for acquiring infrared spectra from the deposited samples. Samples deposited on an optically flat germanium disk with an aluminum backing are transferred to a separate module for reflectance-absorption measurements. The disk is rotated continuously during sample collection, with the result that the chromatogram is deposited as a track near the perimeter of the disk. Rotation of the disk in the spectrometer module allows either a continuous scan of the deposited chromatogram... 

In principle the combination of fibre optics and photodiode array spectrometers shows great advantages in photokinetics. Fibre optic technology allows a wide variation of such set-ups. In the 1960s one tried to achieve a versatile spectrometer by combining modules such as light source, monochromator, cell compartment, and detector on an optical bench. This arrangement of the different components allowed the measurement of absorbance, fluorescence, and reflectance. The same can be achieved nowadays by the use of a so-called simultaneous spectrometer module, schematically presented in Fig. 4.11. 

Fig. 4. Lrft) Schematic of the MCS 2 x 512 VIS color-measuring instrument, consisting of two identical spectrometer modules and the movable measuring head with integrating sphere and flash tube. Right) Measuring setup for the thickness measurement of films and layers, consisting of light source, diode array spectrometer, and fiber bundles (38).

Negligible stray light. Because of the way in which the FT-NIR spectrometer modulates each source wavelength, there is no direct equivalent of the stray light effects found in dispersive spectrometers. 

The precise wavelength adjustment is realized by prism and grating rotation actuated by stepper-motor controlled lever arms. All optical and mechanical spectrometer components are arranged on a rugged base made of cast-iron. A photograph of the DEMON spectrometer module is shown in Figure 3.6. 

The low MW power levels conuuonly employed in TREPR spectroscopy do not require any precautions to avoid detector overload and, therefore, the fiill time development of the transient magnetization is obtained undiminished by any MW detection deadtime. (3) Standard CW EPR equipment can be used for TREPR requiring only moderate efforts to adapt the MW detection part of the spectrometer for the observation of the transient response to a pulsed light excitation with high time resolution. (4) TREPR spectroscopy proved to be a suitable teclmique for observing a variety of spin coherence phenomena, such as transient nutations [16], quantum beats [17] and nuclear modulations [18], that have been usefi.il to interpret EPR data on light-mduced spm-correlated radical pairs. 

The ODMR spectrometer resembles the PA spectrometer shown in Figure 7-1, with the sample placed in a microwave cavity between the pole pieces of an electromagnet. The sample is constantly illuminated by the pump and probe beams amplitude-modulated microwaves arc coupled into the cavity through a waveguide. Changes Si in PL or ST in probe transmission are delected by lock-in am-... 

The surface actlve/surface inactive difference between p-polarlsed/ s-polarised radiation has enabled an alternative modulation technique, polarisation modulation, to be developed (15,16). In electrochemical applications, it allows surface specificity to be achieved whilst working at fixed potential and without electrochemical modulation of the interface. It can be implemented either on EMIRS or on SNIFTIRS spectrometers and can be very valuable in dealing with electrochemically irreversible systems however, the achievable sensitivity falls well short of that obtained with electrochemical modulation. It should also be noted that its "surface specificity" is not truly surface but extends out into the electrolyte with decreasing specificity to about half a wavelength. 

It is only since 1980 that in situ spectroscopic techniques have been developed to obtain identification of the adsorbed intermediates and hence of reliable reaction mechanisms. These new infrared spectroscopic in situ techniques, such as electrochemically modulated infrared reflectance spectroscopy (EMIRS), which uses a dispersive spectrometer, Fourier transform infrared reflectance spectroscopy, or a subtractively normalized interfacial Fourier transform infrared reflectance spectroscopy (SNIFTIRS), have provided definitive proof for the presence of strongly adsorbed species (mainly adsorbed carbon monoxide) acting as catalytic poisons. " " Even though this chapter is not devoted to the description of in situ infrared techniques, it is useful to briefly note the advantages and limitations of such spectroscopic methods. 

In the early work of Bewick and Robinson (1975), a simple monochromator system was used. This is called a dispersive spectrometer. In the experiment the electrode potential was modulated between two potentials, one where the adsorbed species was present and the other where it was absent. Because of the thin electrolyte layer, the modulation frequency is limited to a few hertz. This technique is referred to as electrochemically modulated infrared reflectance spectroscopy (EMIRS). The main problem with this technique is that data acquisition time is long. So it is possible for changes to occur on the electrode surface. 

Mossbauer spectra are usually recorded in transmission geometry, whereby the sample, representing the absorber, contains the stable Mossbauer isotope, i.e., it is not radioactive. A scheme of a typical spectrometer setup is depicted in Fig. 3.1. The radioactive Mossbauer source is attached to the electro-mechanical velocity transducer, or Mossbauer drive, which is moved in a controlled manner for the modulation of the emitted y-radiation by the Doppler effect. The Mossbauer drive is powered by the electronic drive control unit according to a reference voltage (Fr), provided by the digital function generator. Most Mossbauer spectrometers are operated in constant-acceleration mode, in which the drive velocity is linearly swept up and down, either in a saw-tooth or in a triangular mode. In either case. 

Fe which have full width 2r at 0.2 mm s . Other isotopes are less demanding, e.g., Au, for which the lines are ten times wider. Most spectrometers are equipped with electromechanical Mossbauer velocity transducers of the loudspeaker type. This technique is suitable for velocity variations ranging from less than 1 mm s full scale up to several cm s and covers the whole reach of hyperfine splitting for most of the common isotopes. Kalvius, Kankeleit, Cranshaw, and others [1-5] have been pioneers in the field, who laid foundations for the development of high-precision drives with feedback amplifiers for proper linear velocity scales with high stability and low hum. Other techniques for Doppler modulation have been developed for isotopes with extremely narrow hyperfine lines, e.g., Zn. For such isotopes, piezoelectric transducers are mostly used [6, 7], more details of which are found in Sect. 7.2.1. 

In applying RAIRS to CO adsorption, the contribution from CO molecules in the gas phase to the absorption spectrum at CO pressures above 10-3 mbar completely obscures the weak absorption signal of surface adsorbed CO. Beitel et al. found it possible to subtract out the gas phase absorption by coding the surface absorption signal by means of the polarization modulation (PM) technique applied to a conventional RAIRS spectrometer, p-polarised light produces a net surface electric field which can interact with adsorbed molecules, whereas both polarization states are equally sensitive to gas phase absorption because gas phase molecules are randomly oriented. By electronic filtering a differential spectrum is computed which does not show contributions from the gas phase and which has much higher surface sensitivity than a conventional RAIRS setup. 

Mass spectrometers that use electrospray ionization (ESI) do not function well if the eluent contains low volatility salts. This is a major concern when an ion-exchange column is used as a first-dimension column and the salt concentration is used to modulate the retention in this column. In this case, another valve can be connected between the second-dimension column and the detector so that any salt from the second-dimension elution process that is either unretained or weakly retained can be diverted prior to feeding zones to the mass spectrometer. 

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