Polarization modulation signal

On metals in particular, the dependence of the radiation absorption by surface species on the orientation of the electrical vector can be fiilly exploited by using one of the several polarization techniques developed over the past few decades [27, 28, 29 and 30], The idea behind all those approaches is to acquire the p-to-s polarized light intensity ratio during each single IR interferometer scan since the adsorbate only absorbs the p-polarized component, that spectral ratio provides absorbance infonnation for the surface species exclusively. Polarization-modulation mediods provide the added advantage of being able to discriminate between the signals due to adsorbates and those from gas or liquid molecules. Thanks to this, RAIRS data on species chemisorbed on metals have been successfidly acquired in situ under catalytic conditions [31], and even in electrochemical cells [32]. 

Polarization modulation ellipsometers use a photo-elastic modulator to modulate the state of polarization of the incident beam. Polarizer and analyzer are fixed during the measurement. Eourier analysis of the time dependent signal gives the ellipse-... 

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. 

A more complex but faster and more sensitive approach is polarization modulation (PM) IRLD. For such experiments, a photoelastic modulator is used to modulate the polarization state of the incident radiation at about 100 kHz. The detected signal is the sum of the low-frequency intensity modulation with a high-frequency modulation that depends on the orientation of the sample. After appropriate signal filtering, demodulation, and calibration [41], a dichroic difference spectrum can be directly obtained in a single scan. This improves the time resolution to 400 ms, prevents artifacts due to relaxation between measurements, and improves sensitivity for weakly oriented samples. However, structural information can be lost since individual polarized spectra are not recorded. Pezolet and coworkers have used this approach to study the deformation and relaxation in various homopolymers, copolymers, and polymer blends [15,42,43]. For instance, Figure 7 shows the relaxation curves determined in situ for miscible blends of PS and PVME [42]. The (P2) values were determined... 

In polarization modulated ENDOR spectroscopy (PM-ENDOR)45, discussed in Sect. 4.7, the linearly polarized rf field B2 rotates in the laboratory xy-plane at a frequency fr fm, where fm denotes the modulation frequency of the rf carrier. In a PM-ENDOR experiment the same type of cavity, with two rf fields perpendicular to each other, and the same rf level and phase control units used in CP-ENDOR can be utilized. To obtain a rotating, linearly polarized rf field with a constant magnitude B2 and a constant angular velocity Q = 2 fr (fr typically 30-100 Hz), double sideband modulation with a suppressed carrier is applied to both rf signals. With this kind of modulation the phase of the carrier in each channel is switched by 180° for sinQt = 0. In addition, the phases of the two low-frequency envelopes have to be shifted by 90° with respect to each other. The coding of the two rf signals is shown in Fig. 8. 

A variant of IRRAS is polarization modulation IR reflection absorption spectroscopy (PM-IRRAS). In this method, the polarization of the IR beam incident on the sample is modulated between parallel and perpendicular polarization. When the sample is metallic, only the parallel-polarized light yields signals from adsorbed molecules, because the electric field amplitude of perpendicular-polarized light vanishes at the metal surface. This statement is the basis for the metal surface selection rule 100,109). When the medium above the sample (gas or liquid phase) is isotropic, both polarizations are equivalent. The PM-IRRAS method thus enables the measurement of signals from adsorbates on a metal surface in the presence of an absorbing gas or liquid phase. 

The next class of VCD instruments to be developed was centered around a Fourier transform infrared (FT-IR) spectrometer. The idea was to design the sample compartment to be the same as in a dispersive VCD instrument, including a photoelastic modulator. To measure VCD, the detector signal is first sent to a lock-in amplifier to demodulate the high-frequency polarization modulation. The output of the lock-in is a VCD interferogram which is Fourier transformed in much the same way as the ordinary transmission interferogram. 

The in-situ near-normal external reflection results on adsorption of cadmium ions to mixed monolayers are given in Fig. 2b. Since the background spectra are taken for the close-packed mixed monolayers on pure water at each composition, the methylene stretching bands are nearly cancelled out. By contrast, the asymmetric carboxylate band appears with reasonable S/N ratios even without a polarizer-modulator set-up [7], It is noted that the near-normal incidence of the infrared beam resulted in negative signals on the contrary to that of the grazing-angle incidence. 

Sum-frequency generation (SFG) at second-order and the nonlinear Raman spectroscopy BioCARS at fourth-order can also probe chiral molecules. They have no analog in linear optics. We show that both are only symmetry allowed in a fluid, if the fluid is chiral. However, in contrast to optical activity phenomena, these processes arise entirely from induced electric-dipoles (without magnetic or quadrupolar transitions) and they are not circular differential. All laser beams can be linearly polarized and no polarization modulation is required as the detection of a sum-frequency (yiz. five-wave mixing) photon is in itself a measure of the solution s chirality. Since an achiral solvent can not contribute to the signal, these techniques are sensitive, background-free probes of molecular chirality. The SFG... 

Materials Photoacoustic measurements were made on a component-assembled PAS spectrometer consisting of a 9W argon ion laser (Spectra Physics), a 0.5 cc internal volume PAS cell equipped with a sensitive electret microphone (Radio Shack, 3.2 mV/Pa). Circular polarization modulation was achieved with a special low frequency (220 Hz) photoelastic modulator (15) (Hinds International). Signals were detected and processed with a vector tracking lock-in amplifier (PAR model 5204), and intensity modulation was done with a 30-slot blade mechanical chopper (Ortec). Syntheses of all compounds were by well established literature methods. 

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