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B. FTIR Spectrometer14

 The signal-to-noise ratio of FTIR-PAS
measurements
depends on the FTIR spectrometer's performance level as well
as the detector sensitivity and noise level, and signal generation
efficiency of the sample. Low FTIR mirror velocities produce
low modulation frequencies and more efficient signal generation
due to the slow thermal response of samples. Low modulation frequencies
yield higher signal-to-noise spectra for a FTIR's mirror servo-control
system. A high infrared beam intensity is also beneficial and
requires a large source aperture, high source intensity, and
low f number optics. All commercial FTIR systems provide combinations
of these beneficial features to an extent that good FTIR-PAS
measurements can be performed assuming that the FTIR is in good
operating condition.
Typical default operating parameters for FTIR-PAS
measurements with a fast-scan interferometer are given in Table
2.
Table 2. Commonly used FTIR operating parameters
for a fast-scan interferometer.

Mirror velocity = lowest available stable velocity
(0.05, 0.1, 0.25 cm/s are typical)
Resolution = 8 or 16 cm-1
Source aperture = maximum
Spectral Range = 400-4000 cm-1
Number of scans = 32-256

 Mirror velocity
is
given in Table
2 as an optical path difference velocity, v, which allows the
modulation frequency, f, at a given wavenumber, , to be calculated from the formula, . As discussed in the last section, the mirror
velocity can be increased to decrease the sampling depth and
vice versa. Step-scan systems allow a desired modulation frequency
to be selected that is constant at all wavenumbers thus providing
a constant sampling depth for values of absorbance below the
onset of signal saturation.8,11 Resolution
can also be adjusted for specific needs but should not be set
higher than necessary to resolve the structure of interest because
as the resolution is increased, noise will also increase for
a set number of scans. The spectral range is dictated by the
spectrometer's source and beam splitter provided that the photoacoustic
detector window has suitable transparency. In the near-infrared,
visible, and ultraviolet spectral regions, very low mirror velocity
and step-scan interferometers are particularly useful in order
to keep modulation frequencies from becoming too high at the
high wavenumbers of these spectral regions. The signal-to-noise
ratio increases proportional to the square root of the number
of scans, therefore the number of scans can be adjusted to provide
the signal-to-noise ratio necessary for given applications. |