Dissociative Electron Attachment to Hexachlorobenzene. Issue 10 (30th March 2022)

• Record Type: Journal Article
• Authors: Goryunkov, Alexey A.; Asfandiarov, Nail L.; Rakhmeev, Rustam G.; Markova, Angelina V.; Pshenichnyuk, Stanislav A.; Rybalchenko, Alexey V.; Lukonina, Natalia S.; Ioffe, Ilya N.
• Is Part Of: Chemphyschem. Volume 23:Issue 10(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-30
• Subjects: dissociative electron attachment -- hexachlorobenzene -- electron affinity -- cyclic voltammetry -- mass spectrometry; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.202200038
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: Gas phase molecules of hexachlorobenzene (C6 Cl6 ) were investigated by means of dissociative electron attachment spectroscopy (DEAS). Three channels of molecular negative ions decay have been identified: abstraction of Cl − and Cl2 − as well as electron detachment (τ a ∼250 μs at 343 K). All three channels exhibit temperature dependence. The adiabatic electron affinity estimated using a simple but typically accurate Arrhenius model (EA a =1.6–1.9 eV) turns out to be much higher than the quantum‐chemical predictions (EA a =0.9–1.0 eV). We discuss the possible reasons behind the observed discrepancy. Abstract : Gas‐phase electron capture by hexachlorobenzene molecules was investigated by means of DEA spectroscopy. Hexachlorobenzene anions demonstrate three principal decay channels: abstraction of Cl − or Cl2 − and electron autodetachment. The adiabatic electron affinity of C6 Cl6, estimated from the autodetachment kinetics according to a simple yet typically accurate Arrhenius model, turns out to be much higher than the commonly accepted value of about 1.0 eV. This unexpected discrepancy is rationalized in terms of involvement of an intermediate metastable anionic state.