Photoelectron Spectroscopy Study of Quinonimides

Ekram Hossain, Shihu M. Deng, Samer Gozem, Anna I. Krylov, Xue Bin Wang, Paul G. Wenthold

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Structures and energetics of o-, m-, and p-quinonimide anions (OC6H4N-) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, and it is shown that accurate predictions for the electronic structure of the para-quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.

Original languageEnglish (US)
Pages (from-to)11138-11148
Number of pages11
JournalJournal of the American Chemical Society
Volume139
Issue number32
DOIs
StatePublished - Aug 16 2017
Externally publishedYes

Fingerprint

Photoelectron Spectroscopy
Photoelectron spectroscopy
Anions
Negative ions
Ground state
Photoelectrons
Isomers
Electrons
Ions
Electron correlations
Electron affinity
Electronic structure
Spectrum Analysis

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hossain, E., Deng, S. M., Gozem, S., Krylov, A. I., Wang, X. B., & Wenthold, P. G. (2017). Photoelectron Spectroscopy Study of Quinonimides. Journal of the American Chemical Society, 139(32), 11138-11148. https://doi.org/10.1021/jacs.7b05197

Photoelectron Spectroscopy Study of Quinonimides. / Hossain, Ekram; Deng, Shihu M.; Gozem, Samer; Krylov, Anna I.; Wang, Xue Bin; Wenthold, Paul G.

In: Journal of the American Chemical Society, Vol. 139, No. 32, 16.08.2017, p. 11138-11148.

Research output: Contribution to journalArticle

Hossain, E, Deng, SM, Gozem, S, Krylov, AI, Wang, XB & Wenthold, PG 2017, 'Photoelectron Spectroscopy Study of Quinonimides', Journal of the American Chemical Society, vol. 139, no. 32, pp. 11138-11148. https://doi.org/10.1021/jacs.7b05197
Hossain E, Deng SM, Gozem S, Krylov AI, Wang XB, Wenthold PG. Photoelectron Spectroscopy Study of Quinonimides. Journal of the American Chemical Society. 2017 Aug 16;139(32):11138-11148. https://doi.org/10.1021/jacs.7b05197
Hossain, Ekram ; Deng, Shihu M. ; Gozem, Samer ; Krylov, Anna I. ; Wang, Xue Bin ; Wenthold, Paul G. / Photoelectron Spectroscopy Study of Quinonimides. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 32. pp. 11138-11148.
@article{adbf4147e3d346a987c1ba4bbf1b5cbd,
title = "Photoelectron Spectroscopy Study of Quinonimides",
abstract = "Structures and energetics of o-, m-, and p-quinonimide anions (OC6H4N-) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, and it is shown that accurate predictions for the electronic structure of the para-quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.",
author = "Ekram Hossain and Deng, {Shihu M.} and Samer Gozem and Krylov, {Anna I.} and Wang, {Xue Bin} and Wenthold, {Paul G.}",
year = "2017",
month = "8",
day = "16",
doi = "10.1021/jacs.7b05197",
language = "English (US)",
volume = "139",
pages = "11138--11148",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "32",

}

TY - JOUR

T1 - Photoelectron Spectroscopy Study of Quinonimides

AU - Hossain, Ekram

AU - Deng, Shihu M.

AU - Gozem, Samer

AU - Krylov, Anna I.

AU - Wang, Xue Bin

AU - Wenthold, Paul G.

PY - 2017/8/16

Y1 - 2017/8/16

N2 - Structures and energetics of o-, m-, and p-quinonimide anions (OC6H4N-) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, and it is shown that accurate predictions for the electronic structure of the para-quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.

AB - Structures and energetics of o-, m-, and p-quinonimide anions (OC6H4N-) and quinoniminyl radicals have been investigated by using negative ion photoelectron spectroscopy. Modeling of the photoelectron spectrum of the ortho isomer shows that the ground state of the anion is a triplet, while the quinoniminyl radical has a doublet ground state with a doublet-quartet splitting of 35.5 kcal/mol. The para radical has doublet ground state, but a band for a quartet state is missing from the photoelectron spectrum indicating that the anion has a singlet ground state, in contrast to previously reported calculations. The theoretical modeling is revisited here, and it is shown that accurate predictions for the electronic structure of the para-quinonimide anion require both an accurate account of electron correlation and a sufficiently diffuse basis set. Electron affinities of o- and p-quinoniminyl radicals are measured to be 1.715 ± 0.010 and 1.675 ± 0.010 eV, respectively. The photoelectron spectrum of the m-quinonimide anion shows that the ion undergoes several different rearrangements, including a rearrangement to the energetically favorable para isomer. Such rearrangements preclude a meaningful analysis of the experimental spectrum.

UR - http://www.scopus.com/inward/record.url?scp=85027414852&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85027414852&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b05197

DO - 10.1021/jacs.7b05197

M3 - Article

AN - SCOPUS:85027414852

VL - 139

SP - 11138

EP - 11148

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 32

ER -