Spectrometer broadening

We now consider broadening caused by the spectrophotometric system itself. This broadening is of special interest to us in this work because it is not part of the phenomenon under observation. Instead, it represents our inability to observe this phenomenon accurately. Elimination of spectrometer broadening is the usual goal of deconvolution. 

The equivalent width W of an isolated absorption line is independent of spectrometer broadening effects. 

Fig. 3.4.7 The V4 vibration-rotation band of methane (CH4) recorded at high spectral resolution (0.003 cm ). The P-, Q-, and R-branches are indicated, and the lower-state J value is shown for lines in the P- and R-branches. The sample was in a 2.4 m cell at 0.079 mbar and 296 K. Structure in the continuum level is due to variations in the response of the spectrometer. Broadened lines are due to H2O in the optical path.

Each vibrational peak within an electronic transition can also display rotational structure (depending on the spacing of the rotational lines, the resolution of the spectrometer, and the presence or absence of substantial line broadening effects such as... 

The widespread occurrence of long-range couplings in both furanose and pyranose derivatives explains why so many of the P.M.R. spectra of carbohydrate derivatives are apparently poorly resolved, even when the resolution of the spectrometer is above reproach. For example, the Hi resonance of the 1,6-anhydro-D-glucose derivative (12) is coupled to all of the other six ring protons. A further example of the line-broadening effect follows a consideration of the spectrum of 5,6-dideoxy-5,6-epithio-l,2-0-isopropylidene-/ -L-idofuranose for which the half-height... 

It would appear that measurement of the integrated absorption coefficient should furnish an ideal method of quantitative analysis. In practice, however, the absolute measurement of the absorption coefficients of atomic spectral lines is extremely difficult. The natural line width of an atomic spectral line is about 10 5 nm, but owing to the influence of Doppler and pressure effects, the line is broadened to about 0.002 nm at flame temperatures of2000-3000 K. To measure the absorption coefficient of a line thus broadened would require a spectrometer with a resolving power of 500000. This difficulty was overcome by Walsh,41 who used a source of sharp emission lines with a much smaller half width than the absorption line, and the radiation frequency of which is centred on the absorption frequency. In this way, the absorption coefficient at the centre of the line, Kmax, may be measured. If the profile of the absorption line is assumed to be due only to Doppler broadening, then there is a relationship between Kmax and N0. Thus the only requirement of the spectrometer is that it shall be capable of isolating the required resonance line from all other lines emitted by the source. 

A higher-MHz NMR spectrometer is always a better choice, since the sensitivity of the experiment is proportional to the frequency of measurement. Moreover, with highly concentrated solutions, the presence of some solid particles can cause an increase in T) (FID will be short) and line broadening of the NMR signals will result. Therefore, an optimum concentration (say, 25-50 millimolar solution) is recommended. Of course, H-NMR spectra can be readily measured at much lower concentrations, though higher concentrations are necessary for recording - C-NMR spectra. 

We have referred to the various interactions which can cause line broadening in the solid state. One of these, which is normally not a problem in liquid state NMR, is due to the fact that the chemical shift itself is a tensor, i.e. in a coordinate system with orthogonal axes x, y and z its values along these axes can be very different. This anisotropy of the chemical shift is proportional to the magnetic field of the spectrometer (one reason why ultra-high field spectrometers are not so useful), and can lead in solid state spectra to the presence of a series of spinning sidebands, as shown in the spectra of solid polycrystalline powdered triphenylphosphine which follows (Fig. 49). In the absence of spinning, the linewidth of this sample would be around 75 ppm ... 

Since the second-order quadrupolar broadening is inversely proportional to the Larmor frequency [(35) and (36)], one obvious means for improving the resolution is to employ the highest available magnetic field strength [94], The use of several spectrometers operated at different magnetic field strengths can be helpful in... 

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