Single shot laser flash photolysis with a fibre-coupled reference beam monitor.

In the standard nanosecond laser photolysis method for kinetic studies, a Q-switched laser generates transient species, and absorption spectrophotometry provides a measure of their concentrations. The sample is placed between the monitoring source (a pulsed xenon arc or a flash lamp) and a monochromator, and a photomultiplier tube (PMT) is used for measuring the intensity of the light leaving the exit slit of the monochromator. With this (single-beam) arrangement, the laser-induced change in the absorbance of the sample, ΔA, can be calculated only if the intensity of the monitoring beam remains constant during the time interval of interest. When this condition is not fulfilled, a second measurement of the PMT output is made after blocking the path of the laser beam, but shot-to-shot variations in the output of the monitoring source vitiate the analysis when ΔA is small. To overcome this problem, double-beam versions were developed in the last century, but the single-beam version still enjoys greater popularity. With a view to making the double-beam method easily implementable, some simple modifications are introduced, which permit the conversion of an existing laser kinetic spectrometer into a double-beam variant (with one or two monochromators).