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Journal of the Mass Spectrometry Society of Japan
Vol. 64 (2016) No. 1 p. 1-9




The “rule of mass shift” was reexamined for the fragmentation of nitrogen-, sulfur-, or phosphorus-containing functional groups that contain coordinate covalent bonds to oxygen atom(s). A new set of supplementary mass shift values is proposed for the fragmentation of these sulfur and phosphorus compounds, based on the consideration that positively charged, even electron ions with an electron-deficient sulfur or phosphorus atom are regarded as being stable in the gas phase, unlike the case of nitrogen analogues. Several typical modes of bond cleavages of these functional groups are illustrated and discussed.

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