Interferometry, Fourier transform principle

Interferometry is difficult in the uv because of much greater demands on optical alignment and mechanical stabiUty imposed by the shorter wavelength of the radiation (148). In principle any fts interferometer can be operated in the uv when the proper choice of source, beam spHtter, and detector is made, but in practice good performance at wavelengths much shorter than the visible has proved difficult to obtain. Some manufacturers have claimed operating limits of 185 nm, and Fourier transform laboratory instmments have reached 140 nm (145). 

We shall conclude this chapter with a few speculative remarks on possible future developments of nonlinear IR spectroscopy on peptides and proteins. Up to now, we have demonstrated a detailed relationship between the known structure of a few model peptides and the excitonic system of coupled amide I vibrations and have proven the correctness of the excitonic coupling model (at least in principle). We have demonstrated two realizations of 2D-IR spectroscopy a frequency domain (incoherent) technique (Section IV.C) and a form of semi-impulsive method (Section IV.E), which from the experimental viewpoint is extremely simple. Other 2D methods, proposed recently by Mukamel and coworkers (47), would not pose any additional experimental difficulty. In the case of NMR, time domain Fourier transform (FT) methods have proven to be more sensitive by far as a result of the multiplex advantage, which compensates for the small population differences of spin transitions at room temperature. It was recently demonstrated that FT methods are just as advantageous in the infrared regime, although one has to measure electric fields rather than intensities, which cannot be done directly by an electric field detector but requires heterodyned echoes or spectral interferometry (146). Future work will have to explore which experimental technique is most powerful and reliable. 

The principles of interferometry and the operation of an FT-IR instrument are explained in two articles by W. D. Perkins Fourier Transform-Infrared Spectroscopy, Part 1 Instrumentation, Journal of Chemical Education, 63 (January 1986) A5-A10, and Fourier Transform-Infrared Spectroscopy, Part 2 Advantages of FT-IR, Journal of Chemical Education, 64 (November 1987) A269-A271. 

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