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Title: Negative Ion Photoelectron Spectroscopy Confirms the Prediction that D-3h Carbontrioxide (CO 3) Has a Singlet Ground State

Abstract

The CO 3 radical anion (CO 3 •–) has been formed by electrospraying carbonate dianion (CO 3 2–) into the gas phase. The negative ion photoelectron (NIPE) spectrum of CO 3 •– shows that, unlike trimethylenemethane [C(CH 2) 3], carbontrioxide (CO 3) has a singlet ground state. From the NIPE spectrum, the electron affinity of CO 3 was determined to be EA = 4.06 ± 0.03 eV, and the singlet-triplet energy difference was found to be ΔEST = - 17.8 ± 0.9 kcal/mol. B3LYP, CCSD(T), and CASPT2 calculations all find that the two lowest triplet states of CO 3 are very close in energy, a prediction that is confirmed by the relative intensities of the bands in the NIPE spectrum of CO 3 •–. The 560 cm -1 vibrational progression, seen in the low energy region of the triplet band, enables the identification of the lowest, Jahn-Teller-distorted, triplet state as 3A 1, in which both unpaired electrons reside in σ MOs, rather than 3A 2, in which one unpaired electron occupies the b 2 σ MO, and the other occupies the b 1 π MO.

Authors:
 [1];  [2];  [1];  [2];  [1]
  1. Univ. of North Texas, Denton, TX (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1243180
Report Number(s):
PNNL-SA-111484
Journal ID: ISSN 2041-6520; 48584; KC0301050
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 2; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory

Citation Formats

Hrovat, David, Hou, Gao-Lei, Chen, Bo, Wang, Xue B., and Borden, Weston. Negative Ion Photoelectron Spectroscopy Confirms the Prediction that D-3h Carbontrioxide (CO3) Has a Singlet Ground State. United States: N. p., 2015. Web. doi:10.1039/c5sc03542b.
Hrovat, David, Hou, Gao-Lei, Chen, Bo, Wang, Xue B., & Borden, Weston. Negative Ion Photoelectron Spectroscopy Confirms the Prediction that D-3h Carbontrioxide (CO3) Has a Singlet Ground State. United States. doi:10.1039/c5sc03542b.
Hrovat, David, Hou, Gao-Lei, Chen, Bo, Wang, Xue B., and Borden, Weston. Fri . "Negative Ion Photoelectron Spectroscopy Confirms the Prediction that D-3h Carbontrioxide (CO3) Has a Singlet Ground State". United States. doi:10.1039/c5sc03542b. https://www.osti.gov/servlets/purl/1243180.
@article{osti_1243180,
title = {Negative Ion Photoelectron Spectroscopy Confirms the Prediction that D-3h Carbontrioxide (CO3) Has a Singlet Ground State},
author = {Hrovat, David and Hou, Gao-Lei and Chen, Bo and Wang, Xue B. and Borden, Weston},
abstractNote = {The CO3 radical anion (CO3•–) has been formed by electrospraying carbonate dianion (CO32–) into the gas phase. The negative ion photoelectron (NIPE) spectrum of CO3•– shows that, unlike trimethylenemethane [C(CH2)3], carbontrioxide (CO3) has a singlet ground state. From the NIPE spectrum, the electron affinity of CO3 was determined to be EA = 4.06 ± 0.03 eV, and the singlet-triplet energy difference was found to be ΔEST = - 17.8 ± 0.9 kcal/mol. B3LYP, CCSD(T), and CASPT2 calculations all find that the two lowest triplet states of CO3 are very close in energy, a prediction that is confirmed by the relative intensities of the bands in the NIPE spectrum of CO3•–. The 560 cm-1 vibrational progression, seen in the low energy region of the triplet band, enables the identification of the lowest, Jahn-Teller-distorted, triplet state as 3A1, in which both unpaired electrons reside in σ MOs, rather than 3A2, in which one unpaired electron occupies the b2 σ MO, and the other occupies the b1 π MO.},
doi = {10.1039/c5sc03542b},
journal = {Chemical Science},
number = 2,
volume = 7,
place = {United States},
year = {2015},
month = {11}
}

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