Surface dependent hydrogen rearrangement reactions in field ionisation mass spectrometry

Surface dependent hydrogen rearrangement reactions under field ionisation conditions have been investigated. It was not possible to detect surface-induced intramolecular hydrogen rearrangements in molecular ions, in accordance with theoretical expectations. The possibility of intramolecular hydrogen rearrangements exists only for radical ions chemically bound to the emitter surface, for example, the M – H]⁺ ions of the alcohols. The great majority of surfacedependent hydrogen transfer reactions are intermolecular reactions between parts of different molecules or ions bound to the emitter surface. These reactions produce fragment ions, cluster ions and doubly charged ions.