title: Dissociative electron attachment to gas phase valine: a combined experimental and theoretical study.
abstract: Using a crossed electron/molecule beam technique the dissociative electron attachment (DEA) to gas phase L-valine, (CH(3))(2)CHCH(NH(2))COOH, is studied by means of mass spectrometric detection of the product anions. Additionally, ab initio calculations of the structures and energies of the anions and neutral fragments have been carried out at G2MP2 and B3LYP levels. Valine and the previously studied aliphatic amino acids glycine and alanine exhibit several common features due to the fact that at low electron energies the formation of the precursor ion can be characterized by occupation of the pi* orbital of the carboxyl group. The dominant negative ion (M-H)(-) (m/Z=116) is observed at electron energies of 1.12 eV. This ion is the dominant reaction product at electron energies below 5 eV. Additional fragment ions with m/Z=100, 72, 56, 45, 26, and 17 are observed both through the low lying pi* and through higher lying resonances at about 5.5 and 8.0-9.0 eV, which are characterized as core excited resonances. According to the threshold energies calculated here, rearrangements play a significant role in the formation of DEA fragments observed from valine at subexcitation energies.
authors.affiliation: Department of Experimental Physics, Faculty of Mathematics, Physics and Informatics, Comenius University, Mlynská dolina F2, 84248 Bratislava, Slovakia.
authors.forename: Peter
authors.initials: P
authors.lastname: Papp
authors.forename: Jan
authors.initials: J
authors.lastname: Urban
authors.forename: Stefan
authors.initials: S
authors.lastname: Matejcík
authors.forename: Michal
authors.initials: M
authors.lastname: Stano
authors.forename: Oddur
authors.initials: O
authors.lastname: Ingolfsson
mesh_terms: D003198:Computer Simulation; D004579:Electron Transport; D004583:Electrons; D005740:Gases / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D044367:Phase Transition; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D014633:Valine / Q000737:chemistry*
chemical_list: D005740:Gases; D014633:Valine