Abstract

A high resolution mass spectrometer has been used to obtain precise atomic mass differences by means of an improved peak-matching technique in which off-line computer analysis is used to determine the matching condition. The procedure retains the improved signal-to-noise ratio achieved with a signal averager, but offers improved precision in a given operating time and removes further human judgment of the matched condition. Moreover, it makes possible a comparison between the precision obtained experimentally and the theoretical limit (derived here) determined by the instrument resolution and the number of ions detected. Representative results for doublet spacings are presented for which the precision (δ M/M ∼ 5 × 10 −9) approaches the statistical limit.

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