Polyatomic ions in mass spectrometry

The mass determination of ionic species (atomic or polyatomic ions) in mass spectrometry is always a comparative measurement, which means the mass of an ionic species is determined with respect to reference masses of elements (or substances) used for mass calibration. The reference mass is thus acquired from the mass unit (m = In = 1/12) of the mass of the neutral carbon isotope (m = 1.66 X 10 kg). A mass calibration is easy to perform in solid-state mass spectrometry if the sample contains carbon (using carbon cluster ions with whole masses, as discussed above). The so-called doublet method was apphed formerly, e.g., ions and doubly charged Mg + forming a doublet at the same nominal mass number 12 were considered, where they are slightly displaced with respect to one another. The doublet method is no longer of relevance in modern inorganic mass spectrometry. Orientation in the mass spectra can be carried out via the matrix, minor and trace elements after mass calibration and by comparing the measured isotopic pattern of elements with theoretical values. 

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