Low-lying electronic states of cyclopentadienone

Dmitry Khuseynov, John F. Stanton, Andrei M Sanov

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

We report a combined experimental and theoretical study of the low-lying electronic states of cyclopentadienone (C5H4O). The cyclopentadienone anion (C5H4O-) was generated in the gas phase via reaction of atomic oxygen radical anions (O-) with cyclopentanone (C5H8O). Photoelectron imaging was used to gain access to the first three electronic states of C5H 4O, including the X 1A1 ground state and the 3B2 and 3A2 excited states. The first two state assignments are supported by the Franck-Condon simulations of the vibrational progressions observed in the X 1A1 and 3B2 bands in the photoelectron spectra. The adiabatic electron affinity of cyclopentadienone in the ground state is determined to be EA(X 1A1) = 1.06 ± 0.01 eV, and the corresponding values for the first two excited states are EA(3B2) = 2.56 ± 0.02 eV and EA(3A2) = 3.45 ± 0.01 eV. These experimental determinations are in excellent agreement with the CCSD(T) theory predictions, lending further confidence to the above state assignments. On the basis of these results, the lowest singlet-triplet splitting (between the X 1A1 and 3B2 states) in cyclopentadienone is ΔES-T = 1.50 ± 0.02 eV.

Original languageEnglish (US)
Pages (from-to)6965-6970
Number of pages6
JournalJournal of Physical Chemistry A
Volume118
Issue number34
DOIs
StatePublished - 2014

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State assignment
Electronic states
Photoelectrons
Excited states
Ground state
Anions
photoelectrons
Signal filtering and prediction
anions
Electron affinity
ground state
electron affinity
electronics
progressions
excitation
confidence
Reactive Oxygen Species
Gases
vapor phases
Imaging techniques

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Low-lying electronic states of cyclopentadienone. / Khuseynov, Dmitry; Stanton, John F.; Sanov, Andrei M.

In: Journal of Physical Chemistry A, Vol. 118, No. 34, 2014, p. 6965-6970.

Research output: Contribution to journalArticle

Khuseynov, Dmitry ; Stanton, John F. ; Sanov, Andrei M. / Low-lying electronic states of cyclopentadienone. In: Journal of Physical Chemistry A. 2014 ; Vol. 118, No. 34. pp. 6965-6970.
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AB - We report a combined experimental and theoretical study of the low-lying electronic states of cyclopentadienone (C5H4O). The cyclopentadienone anion (C5H4O-) was generated in the gas phase via reaction of atomic oxygen radical anions (O-) with cyclopentanone (C5H8O). Photoelectron imaging was used to gain access to the first three electronic states of C5H 4O, including the X 1A1 ground state and the 3B2 and 3A2 excited states. The first two state assignments are supported by the Franck-Condon simulations of the vibrational progressions observed in the X 1A1 and 3B2 bands in the photoelectron spectra. The adiabatic electron affinity of cyclopentadienone in the ground state is determined to be EA(X 1A1) = 1.06 ± 0.01 eV, and the corresponding values for the first two excited states are EA(3B2) = 2.56 ± 0.02 eV and EA(3A2) = 3.45 ± 0.01 eV. These experimental determinations are in excellent agreement with the CCSD(T) theory predictions, lending further confidence to the above state assignments. On the basis of these results, the lowest singlet-triplet splitting (between the X 1A1 and 3B2 states) in cyclopentadienone is ΔES-T = 1.50 ± 0.02 eV.

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