SAMPLE MODULATION SPECTROMETRY WITH A STEP-SCAN INTERFEROMETER

SAMPLE MODULATION SPECTROMETRY WITH A STEP-SCAN INTERFEROMETER... 

In Chapter 20 we saw how photoacoustic (PA) spectra could be measured with a step-scan interferometer no matter whether the PA signal was demodulated with a lock-in amplifier or by digital signal processing (DSP). For DSP, a Fourier transform (FT) has the same function as the lock-in amplifier. Manning et al. [14] showed that the same approach is feasible in DIRLD spectrometry with a step-scan FT-IR spectrometer but without a PEM. Consider the case where the detector signal contains components caused by simultaneous sinusoidal phase modulation at frequency /pm, and sample modulation at frequency fs. The phase- and sample-modulated components of the signal can be demodulated either with a... 

Rapid reversible processes can be studied by FT-IR spectrometry in at least four ways, two using rapid-scan interferometers and two using step-scan interferometers. Three of these approaches, asynchronous sampling and stroboscopic measurements with a rapid-scan interferometer and time-resolved spectroscopy with a step-scan interferometer, were described in Sections 19.2 and 19.3. The fourth approach involves the use of a step-scan interferometer and some type of sample modulation. We have seen one application in the earlier part of this chapter, and two other applications will now be described. The reorientation of liquid crystals induced by rapid switching of the electric field to which they are being subjected has been studied by at least three of these approaches. Results have been summarized in an excellent article by Czamecki [17]. In this section we discuss the application of sample-modulation FT-IR spectrometry to this problem. 

No matter what modulation frequency is used for PA/FT-IR spectrometry, the bands from the upper layers of the sample always dominate the spectrum. In addition, the fact that the thermal wave decay length varies as when the spectra are measured with a rapid-scanning interferometer has always led to suboptimal results. The variation of L with wavenumber may be circumvented through the use of a phase-modulated step-scan interferometer, and most contemporary PA/FT-IR spectra are now measured with this type of instrument. 

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