Time resolved photodissociation of small peptide ions

A new instrument has been constructed whose purpose is to study time-resolved photodissociation (TRPD) of small peptide ions. Laser desorption of neutral peptides is combined with laser photoionization in an ion trap followed by thermalization, laser photodissociation and time of flight mass analysis. Ionization and excitation take place through an aromatic chromophore at the C-terminus of the peptide whereas dissociation produces the immonium ion at the N-terminus. The long-range purpose is to uncover the role of IVR in unimolecular fragmentations of peptide radical cations. One avenue is the determination of microcanonical rate constants at a well-defined internal energy E for a series of peptides possessing the same chromophore, undergoing the same fragmentation but having a variable number of degrees of freedom. This paper demonstrates the feasibility of the method and provides the first attempts at rate measurements for the peptide leucyl tyrosine (LeuTyr). Received 6 January 2002 Published online 13 September 2002