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Selectivity in fragmentation of N-methylacetamide after resonant K-shell excitation

Journal article
Authors Peter Salen
Magdalena Kaminska
Richard J. Squibb
Robert Richter
Michele Alagia
Stefano Stranges
Peter van der Meulen
John H. D. Eland
Raimund Feifel
Vitali Zhaunerchyk
Published in Physical Chemistry Chemical Physics - PCCP
Volume 16
Issue 29
Pages 15231-15240
ISSN 1463-9076
Publication year 2014
Published at Department of Physics (GU)
Pages 15231-15240
Language en
Subject categories Atom and Molecular Physics and Optics


The fragmentation pattern of the peptide model system, N-methylacetamide, is investigated using ion time-of-flight (TOF) spectroscopy after resonant K-shell excitation. Corresponding near-edge X-ray absorption fine structure (NEXAFS) spectra recorded at high resolution at the C1s, N1s and O1s edges are presented. Analysis of the ion TOF data reveals a multitude of fragmentation channels and dissociation pathways. Comparison between the excitation of six different resonances in the vicinity of the C1s, N1s and O1s edges suggests evidence for site-selective bond breaking. In particular the breaking of the peptide bond and the N–C bond show a clear correlation with resonant excitation at the N1s edge. Also, stronger tendencies towards site-selective bond breaking are found for the generation of single ions compared with ion pairs. Analysis of angular distributions of ions from breakage of the peptide bond yields a fragmentation time of <400 fs.

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