Pulsed hollow-cathode background correction

Background correction using a pulsed hollow cathode lamp... 

Figure 14.15—Pulsed hollow cathode lamp background correction, a) Shape of the emission line from a hollow cathode lamp under normal operating conditions, b) the 4000 Smith-Hieftje model from Thermo Jarrell Ash uses the principle of pulsed-source correction. The mercury source and the retractable mirrors are used for calibration of the monochromator. (Reproduced by permission of Thermo Jarrell Ash.)...

When the intensity of a hollow cathode lamp increases because of a reduction in the shunt resistance, the profile of the emission line changes. As the central part of the cathode becomes very hot, the line is broadened for several reasons. However, vaporised atoms emitted by the cathode will reabsorb in a colder part of the lamp in the form of a very fine line. The net result is that the emission curve dips in the middle because of self-absorption. This observation is the basis of the pulsed lamp technique for correction of background absorption (Fig. 14.15). 

Smith-Hieftje background correction uses a single hollow-cathode lamp pulsed with first a low current and then a high current. The low-current mode obtains the total absorbance, while the background is estimated during the high-current pulse. Read the interview at the beginning of Part V to learn more about Cary Hieftje and his work. 

Pulsed lamp background correction A very simple method of background correction has been proposed by Smith and Hieftje [25] and is therefore known as the Smith—Hieftje method. It is based on the self-reversal behaviour of the radiation emitted by hollow cathode lamps when they are operated at high currents. This ef feet is seen when a large number of non-excited atoms are brought into the vapor phase. These atoms absorb the characteristic radiation emitted by the excited species. At the same time, a significant broadening of the emission line is observed. 

Background correction is thus achieved by modulating the lamp current to generate a longer pulse at low current (e. g. 9 ms at 5—10 mA), followed directly by a short pulse at high lamp current (for example, 0.3 ms at 200—300 mA). As the atom cloud persists in the hollow cathode lamp for several milliseconds, a minimum pulse repetition time of typically 50 ms is required to allow the atom cloud to clear before the next measurement cycle is started. 

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