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Title: Electron attachment to indole and related molecules

Abstract

Gas-phase formation of temporary negative ion states via resonance attachment of low-energy (0–6 eV) electrons into vacant molecular orbitals of indoline (I), indene (II), indole (III), 2-methylen-1,3,3-trimethylindoline (IV), and 2,3,3-trimethyl-indolenine (V) was investigated for the first time by electron transmission spectroscopy (ETS). The description of their empty-level structures was supported by density functional theory and Hartree-Fock calculations, using empirically calibrated linear equations to scale the calculated virtual orbital energies. Dissociative electron attachment spectroscopy (DEAS) was used to measure the fragment anion yields generated through dissociative decay channels of the parent molecular anions of compounds I-V, detected with a mass filter as a function of the incident electron energy in the 0–14 eV energy range. The vertical and adiabatic electron affinities were evaluated at the B3LYP/6-31+G(d) level as the anion/neutral total energy difference. The same theoretical method is also used for evaluation of the thermodynamic energy thresholds for production of the negative fragments observed in the DEA spectra. The loss of a hydrogen atom from the parent molecular anion ([M-H]{sup −}) provides the most intense signal in compounds I-IV. The gas-phase DEAS data can provide support for biochemical reaction mechanisms in vivo involving initial hydrogen abstraction from the nitrogen atom ofmore » the indole moiety, present in a variety of biologically important molecules.« less

Authors:
 [1];  [2]
  1. Dipartimento di Chimica “G. Ciamician”, Universitá di Bologna, via Selmi 2, 40126 Bologna (Italy)
  2. ISOF, Istituto per la Sintesi Organica e la Fotoreattività, C.N.R., via Gobetti 101, 40129 Bologna (Italy)
Publication Date:
OSTI Identifier:
22251483
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 139; Journal Issue: 18; Other Information: (c) 2013 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; DENSITY FUNCTIONAL METHOD; ELECTRON ATTACHMENT; EVALUATION; HARTREE-FOCK METHOD; HYDROGEN; IN VIVO; INDENE; INDOLES; SPECTRA; SPECTROSCOPY

Citation Formats

Modelli, Alberto, Centro Interdipartimentale di Ricerca in Scienze Ambientali, Jones, Derek, and Pshenichnyuk, Stanislav A., E-mail: sapsh@anrb.ru. Electron attachment to indole and related molecules. United States: N. p., 2013. Web. doi:10.1063/1.4829057.
Modelli, Alberto, Centro Interdipartimentale di Ricerca in Scienze Ambientali, Jones, Derek, & Pshenichnyuk, Stanislav A., E-mail: sapsh@anrb.ru. Electron attachment to indole and related molecules. United States. https://doi.org/10.1063/1.4829057
Modelli, Alberto, Centro Interdipartimentale di Ricerca in Scienze Ambientali, Jones, Derek, and Pshenichnyuk, Stanislav A., E-mail: sapsh@anrb.ru. 2013. "Electron attachment to indole and related molecules". United States. https://doi.org/10.1063/1.4829057.
@article{osti_22251483,
title = {Electron attachment to indole and related molecules},
author = {Modelli, Alberto and Centro Interdipartimentale di Ricerca in Scienze Ambientali and Jones, Derek and Pshenichnyuk, Stanislav A., E-mail: sapsh@anrb.ru},
abstractNote = {Gas-phase formation of temporary negative ion states via resonance attachment of low-energy (0–6 eV) electrons into vacant molecular orbitals of indoline (I), indene (II), indole (III), 2-methylen-1,3,3-trimethylindoline (IV), and 2,3,3-trimethyl-indolenine (V) was investigated for the first time by electron transmission spectroscopy (ETS). The description of their empty-level structures was supported by density functional theory and Hartree-Fock calculations, using empirically calibrated linear equations to scale the calculated virtual orbital energies. Dissociative electron attachment spectroscopy (DEAS) was used to measure the fragment anion yields generated through dissociative decay channels of the parent molecular anions of compounds I-V, detected with a mass filter as a function of the incident electron energy in the 0–14 eV energy range. The vertical and adiabatic electron affinities were evaluated at the B3LYP/6-31+G(d) level as the anion/neutral total energy difference. The same theoretical method is also used for evaluation of the thermodynamic energy thresholds for production of the negative fragments observed in the DEA spectra. The loss of a hydrogen atom from the parent molecular anion ([M-H]{sup −}) provides the most intense signal in compounds I-IV. The gas-phase DEAS data can provide support for biochemical reaction mechanisms in vivo involving initial hydrogen abstraction from the nitrogen atom of the indole moiety, present in a variety of biologically important molecules.},
doi = {10.1063/1.4829057},
url = {https://www.osti.gov/biblio/22251483}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 18,
volume = 139,
place = {United States},
year = {Thu Nov 14 00:00:00 EST 2013},
month = {Thu Nov 14 00:00:00 EST 2013}
}