Abstract

Accurate quantitative measurements of desorption rates or adsorbate coverages in thermal desorption mass spectroscopy (TDS) using line-of-sight mass spectrometers are hindered by the fact that the angular distributions of desorption flux can vary widely from desorbate to desorbate, ranging from cos 1ø to cos 9 ø for most species studied to date (ø = polar angle from surface normal). These differences can easily lead to errors exceeding 400% in measuring the relative desorption rates of different species. We show here that, by placing the mass spectrometer's ion source or entrance aperture at a “magic-angle” ø mthese errors can be reduced to less than 26% maximum deviation (or ± 7% standard deviation). Depending upon the sample-to-detector distance, ø m varies from ~ 42° to 34°. It is recommended that TDS experiments be performed at this “magic-angle” for improvement in the quantitative accuracy of coverage or rate measurements.

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