Experimental and theoretical investigations of isomerization reactions of ionized acetone and its dimer

Yoshiyuki Matsuda, Kunihito Hoki, Satoshi Maeda, Ken Ichi Hanaue, Keisuke Ohta, Keiji Morokuma, Naohiko Mikami, Asuka Fujii

Research output: Contribution to journalArticlepeer-review

15 Citations (Scopus)

Abstract

Ionization dynamics of acetone and its dimer in supersonic jets is investigated by a combination of experimental and theoretical techniques, both of which have recently been developed. In experiments, the neutral and the cationic structures are explored by infrared predissociation spectroscopy with the vacuum-ultraviolet photoionization detection schemes. Reaction paths following the one-photon ionization of the acetone monomer and its dimer have been studied by the joint use of several theoretical methods including the ab initio molecular dynamics, the global reaction route mapping, the intrinsic reaction coordinate, and the artificial force induced reaction calculations. Upon one-photon ionization, the dimer isomerizes to the H-bonded form, in which the enol cation of acetone is bound to the neutral molecule, while this enolization is energetically forbidden in the acetone monomer. The enolization of the dimer cation occurs through a two-step proton-transfer from the methyl group of the ionized moiety, and is catalyzed by the neutral moiety within the dimer cation.

Original languageEnglish
Pages (from-to)712-719
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume14
Issue number2
DOIs
Publication statusPublished - 2012 Jan 14

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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