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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.

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [2]; ORCiD logo [1]
  1. The Department of Chemistry Purdue University West Lafayette, Indiana 47906, United States
  2. Physical Sciences Division, Pacific Northwest National Laboratory P.O. Box 999, MS k8-88 Richland, Washington 99352, United States
  3. Department of Chemistry University of Southern California Los Angeles, 90089, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1398183
Report Number(s):
PNNL-SA-126328
Journal ID: ISSN 0002-7863; 48585; KC0301050
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 32
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Hossain, Ekram, Deng, Shihu M., Gozem, Samer, Krylov, Anna I., Wang, Xue-Bin, and Wenthold, Paul G. Photoelectron Spectroscopy Study of Quinonimides. United States: N. p., 2017. Web. doi: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. United States. doi:10.1021/jacs.7b05197.
Hossain, Ekram, Deng, Shihu M., Gozem, Samer, Krylov, Anna I., Wang, Xue-Bin, and Wenthold, Paul G. Thu . "Photoelectron Spectroscopy Study of Quinonimides". United States. doi:10.1021/jacs.7b05197.
@article{osti_1398183,
title = {Photoelectron Spectroscopy Study of Quinonimides},
author = {Hossain, Ekram and Deng, Shihu M. and Gozem, Samer and Krylov, Anna I. and Wang, Xue-Bin and Wenthold, Paul G.},
abstractNote = {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.},
doi = {10.1021/jacs.7b05197},
journal = {Journal of the American Chemical Society},
number = 32,
volume = 139,
place = {United States},
year = {Thu Aug 03 00:00:00 EDT 2017},
month = {Thu Aug 03 00:00:00 EDT 2017}
}