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Multiphoton ionization of inner-valence electrons and fragmentation of polyatomic molecules

The ionization of inner valence electrons are responsible for the fragmentation of polyatomic molecules in strong laser fields. According to a qualitative model the dissociation of the molecules occurs through a three-step mechanism:

The short pulse induced molecular fragmentation may be used as an ion source for high performance mass spectroscopy. The selectivity provided by a short pulse based source is superior to that expected when using the conventional electron ionization based sources, in particular when the identification of optical isomers is required.