Design of a simple cryogenic system for ultraviolet-visible absorption spectroscopy with a back-reflectance fiber optic probe.

We report a convenient and inexpensive technique for the rapid acquisition of absorption spectra from small samples at cryogenic temperatures using a home built cryostat with novel collection optics. A cylindrical copper block was constructed with a coaxial bore to hold a 4.00 mm diameter electron paramagnetic resonance (EPR) tube and mounted on a copper feed in thermal contact with liquid nitrogen. A 6.35 mm diameter hole was bored into the side of the cylinder so a fiber optic cable bundle could be positioned orthogonally to the EPR tube. The light passing through the sample is reflected off of the opposing surfaces of the EPR tube and surrounding copper, back through the sample. The emergent light is then collected using the fiber optic bundle and analyzed using a dispersive spectrometer. Absorption spectra for KMnO4 were measured between 400 and 700 nm. Absorption intensity at 506, 525, 545, and 567 nm was found to be proportional to concentration, displaying Beer's law-like behavior. The EPR tube had an internal diameter of 3.2 mm; the double pass of the probe beam through the sample affords a central path length of about 6.4 mm. Comparing these measurements with those recorded on a conventional tabletop spectrometer using a cuvette with a 10.00 mm path length, we consistently found a ratio between intensities of 0.58 rather than the anticipated 0.64. These 6% smaller values we attribute to the curvature of the EPR tube and transmission/reflection losses. This system is particularly well-suited to studying the kinetics and dynamics of chemical reactions at cryogenic temperatures. The rapid response (100 ms) and multiplex advantage provided the opportunity of recording simultaneous time courses at several wavelengths following initiation of a chemical reaction with a pulsed laser source.