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

Hrovat, David; Hou, Gao-Lei; Chen, Bo; Wang, Xue B.; Borden, Weston

doi:10.1039/c5sc03542b

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

Journal Article · Fri Nov 13 00:00:00 EST 2015 · Chemical Science

DOI:https://doi.org/10.1039/c5sc03542b· OSTI ID:1243180

Hrovat, David ^[1]; Hou, Gao-Lei ^[2]; Chen, Bo ^[1]; Wang, Xue B. ^[2]; Borden, Weston ^[1]

Univ. of North Texas, Denton, TX (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

The CO₃ radical anion (CO₃^•–) has been formed by electrospraying carbonate dianion (CO₃^2–) 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.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1243180

Report Number(s):: PNNL-SA-111484; 48584; KC0301050

Journal Information:: Chemical Science, Vol. 7, Issue 2; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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