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Title: Negative Ion Photoelectron Spectroscopy Confirms the Prediction that D-3h Carbontrioxide (CO3) Has a Singlet Ground State

Abstract

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.

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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