title: Models of fragmentations induced by electron attachment to protonated peptides.
abstract: Invoking a number of theoretical levels ranging from HF/STO-3G to CCSD(T)/aug-cc-pVQZ, we have made a detailed survey of six potential energy surfaces (NH4+, NH4*, [CH3CONHCH3]H+, [CH3CONHCH3]H*, [HCONHCH2CONH2]H+, [HCONHCH2CONH2]H*). In conjunction with this, ab inito direct dynamics calculations have been conducted, tracing out several hundred reaction trajectories to reveal details of the electron-capture dissociation mechanism. The model calculations suggest the possibility of a bimodal pattern where some of the radicals, formed upon recombination, dissociate almost directly within one picosecond, the remaining radicals being subject to complete energy redistribution with a subsequent dissociation occurring at the microsecond timescale. Both processes give rise to c and z backbone fragments, resulting from cleavage of N-Calpha bonds of the peptide chain.
authors.affiliation: Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, N-0315 Oslo, Norway.
authors.forename: Vebjørn
authors.initials: V
authors.lastname: Bakken
authors.forename: Trygve
authors.initials: T
authors.lastname: Helgaker
authors.forename: Einar
authors.initials: E
authors.lastname: Uggerud
mesh_terms: D004583:Electrons; D008956:Models, Chemical; D010446:Peptide Fragments / Q000737:chemistry; D010455:Peptides / Q000737:chemistry*; D011522:Protons; D021241:Spectrometry, Mass, Electrospray Ionization; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
chemical_list: D010446:Peptide Fragments; D010455:Peptides; D011522:Protons