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

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.

View Accepted Manuscript (DOE)

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

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Friedrich Hund and Chemistry Kutzelnigg, Werner Angewandte Chemie International Edition in English, Vol. 35, Issue 6 https://doi.org/10.1002/anie.199605721	journal	April 1996
The Lowest Singlet and Triplet States of the Oxyallyl Diradical Ichino, Takatoshi; Villano, Stephanie M.; Gianola, Adam J. Angewandte Chemie International Edition, Vol. 48, Issue 45 https://doi.org/10.1002/anie.200904417	journal	October 2009
Identification of the D3h Isomer of Carbon Trioxide (CO3) and Its Implications for Atmospheric Chemistry Jamieson, Corey S.; Mebel, Alexander M.; Kaiser, Ralf I. ChemPhysChem, Vol. 7, Issue 12 https://doi.org/10.1002/cphc.200600390	journal	October 2006
The structure of carbon trioxide Pople, John A.; Seeger, Ute; Seeger, Rolf Journal of Computational Chemistry, Vol. 1, Issue 2 https://doi.org/10.1002/jcc.540010215	journal	July 1980
AB initio calculation of the structure of the CO3 molecule Cornille, M.; Horsley, J. Chemical Physics Letters, Vol. 6, Issue 4 https://doi.org/10.1016/0009-2614(70)85097-7	journal	August 1970
A theoretical study of the structure and properties of carbon trioxide Sabin, J. R.; Kim, H. Chemical Physics Letters, Vol. 11, Issue 5 https://doi.org/10.1016/0009-2614(71)87010-0	journal	November 1971
Many-body perturbation theory and coupled-cluster calculations of the ground-state structure of CO3 Castro, Marcos A.; Canuto, Sylvio; Simas, Alfredo M. Chemical Physics Letters, Vol. 177, Issue 1 https://doi.org/10.1016/0009-2614(91)90182-9	journal	February 1991
The second-order Jahn-Teller effect Pearson, Ralph G. Journal of Molecular Structure: THEOCHEM, Vol. 103 https://doi.org/10.1016/0166-1280(83)85006-4	journal	August 1983
Ab initio calculation of the ground state of carbon trioxide in D3h symmetry and the E′ distortion to C2v symmetry Van De Guchte, W. J.; Zwart, J. P.; Mulder, J. J. C. Journal of Molecular Structure: THEOCHEM, Vol. 152, Issue 3-4 https://doi.org/10.1016/0166-1280(87)80062-3	journal	July 1987
A theoretical study of the force field for carbon trioxide Francisco, J. S.; Williams, I. H. Chemical Physics, Vol. 95, Issue 3 https://doi.org/10.1016/0301-0104(85)80160-9	journal	May 1985
A fifth-order perturbation comparison of electron correlation theories Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A. Chemical Physics Letters, Vol. 157, Issue 6 https://doi.org/10.1016/S0009-2614(89)87395-6	journal	May 1989
Singlet and triplet states of the CO3 and CO4 molecules Averyanov, A. S.; Khait, Yu. G.; Puzanov, Yu. V. Journal of Molecular Structure: THEOCHEM, Vol. 459, Issue 1-3 https://doi.org/10.1016/S0166-1280(98)00261-9	journal	February 1999
Photoelectron spectroscopy of the trimethylenemethane negative ion Wenthold, Paul G.; Hu, Jun; Squires, Robert R. Journal of the American Society for Mass Spectrometry, Vol. 10, Issue 9 https://doi.org/10.1016/S1044-0305(99)00043-4	journal	September 1999
On the formation of higher carbon oxides in extreme environments Kaiser, Ralf I.; Mebel, Alexander M. Chemical Physics Letters, Vol. 465, Issue 1-3 https://doi.org/10.1016/j.cplett.2008.07.076	journal	November 2008
Production and utilization of CO3− produced by a corona discharge in air for atmospheric pressure chemical ionization Ewing, Robert G.; Waltman, Melanie J. International Journal of Mass Spectrometry, Vol. 296, Issue 1-3 https://doi.org/10.1016/j.ijms.2010.08.024	journal	September 2010
DFT and TDDFT study of carbon trioxide Qin, Changyong; Soo, Tsz-Yan Journal of Molecular Structure: THEOCHEM, Vol. 897, Issue 1-3 https://doi.org/10.1016/j.theochem.2008.11.018	journal	March 2009
The Importance of Including Dynamic Electron Correlation in ab Initio Calculations Borden, Weston Thatcher; Davidson, Ernest R. Accounts of Chemical Research, Vol. 29, Issue 2 https://doi.org/10.1021/ar950134v	journal	January 1996
Pseudo-Jahn–Teller Effect—A Two-State Paradigm in Formation, Deformation, and Transformation of Molecular Systems and Solids Bersuker, Isaac B. Chemical Reviews, Vol. 113, Issue 3 https://doi.org/10.1021/cr300279n	journal	January 2013
Combined Jahn−Teller and Pseudo-Jahn−Teller Effect in the CO ₃ Molecule: A Seven-State Six-Mode Problem Liu, Yang; Bersuker, Isaac B.; Zou, Wenli Journal of Chemical Theory and Computation, Vol. 5, Issue 10 https://doi.org/10.1021/ct9002515	journal	August 2009
Features of the lowest singlet and triplet potential energy surfaces of carbonate radical Froese, Robert D. J.; Goddard, John D. The Journal of Physical Chemistry, Vol. 97, Issue 29 https://doi.org/10.1021/j100131a016	journal	July 1993
Symmetry breaking in polyatomic molecules: real and artifactual Davidson, Ernest R.; Borden, Weston Thatcher The Journal of Physical Chemistry, Vol. 87, Issue 24 https://doi.org/10.1021/j150642a005	journal	November 1983
Ab initio calculations on m-quinone. The ground state is a triplet Fort, Raymond C.; Getty, Stephen J.; Hrovat, David A. Journal of the American Chemical Society, Vol. 114, Issue 19 https://doi.org/10.1021/ja00045a031	journal	September 1992
Effects of electron repulsion in conjugated hydrocarbon diradicals Borden, Weston Thatcher; Davidson, Ernest R. Journal of the American Chemical Society, Vol. 99, Issue 14 https://doi.org/10.1021/ja00456a010	journal	June 1977
Symmetry rule for predicting molecular structures Pearson, Ralph G. Journal of the American Chemical Society, Vol. 91, Issue 18 https://doi.org/10.1021/ja01046a001	journal	August 1969
Molecular geometry and electronic structure of carbon trioxide Olsen, John F.; Burnelle, Louis Journal of the American Chemical Society, Vol. 91, Issue 26 https://doi.org/10.1021/ja01054a015	journal	December 1969
Negative Ion Photoelectron Spectroscopy Confirms the Prediction that (CO) ₅ and (CO) ₆ Each Has a Singlet Ground State Bao, Xiaoguang; Hrovat, David A.; Borden, Weston Thatcher Journal of the American Chemical Society, Vol. 135, Issue 11 https://doi.org/10.1021/ja4005128	journal	March 2013
The Negative Ion Photoelectron Spectrum of meta -Benzoquinone Radical Anion (MBQ ^•– ): A Joint Experimental and Computational Study Chen, Bo; Hrovat, David A.; Deng, S. H. M. Journal of the American Chemical Society, Vol. 136, Issue 9 https://doi.org/10.1021/ja412433t	journal	February 2014
Photoelectron Spectroscopy of the Trimethylene- methane Negative Ion. The Singlet−Triplet Splitting of Trimethylenemethane ^† Wenthold, Paul G.; Hu, Jun; Squires, Robert R. Journal of the American Chemical Society, Vol. 118, Issue 2 https://doi.org/10.1021/ja9532547	journal	January 1996
Photoelectron Spectroscopy of m -Xylylene Anion Wenthold, Paul G.; Kim, Joseph B.; Lineberger, W. C. Journal of the American Chemical Society, Vol. 119, Issue 6 https://doi.org/10.1021/ja9623830	journal	February 1997
Negative Ion Photoelectron Spectroscopy Confirms the Prediction that 1,2,4,5-Tetraoxatetramethylenebenzene Has a Singlet Ground State Hrovat, David A.; Hou, Gao-Lei; Wang, Xue-Bin Journal of the American Chemical Society, Vol. 137, Issue 28 https://doi.org/10.1021/jacs.5b04416	journal	July 2015
Symmetry Breaking and the Molecular Structure of NO ₃ ⁺ ^† Miller, Charles E.; Francisco, Joseph S. The Journal of Physical Chemistry A, Vol. 105, Issue 9 https://doi.org/10.1021/jp002349e	journal	March 2001
Theoretical Study of Oxygen Isotope Exchange and Quenching in the O( ¹ D) + CO ₂ Reaction ^† Mebel, A. M.; Hayashi, M.; Kislov, V. V. The Journal of Physical Chemistry A, Vol. 108, Issue 39 https://doi.org/10.1021/jp049315h	journal	September 2004
Electronic Structure of Carbon Trioxide and Vibronic Interactions Involving Jahn−Teller States Kowalczyk, Timothy; Krylov, Anna I. The Journal of Physical Chemistry A, Vol. 111, Issue 33 https://doi.org/10.1021/jp073627d	journal	August 2007
Photoelectron Spectroscopic Study of the Oxyallyl Diradical Ichino, Takatoshi; Villano, Stephanie M.; Gianola, Adam J. The Journal of Physical Chemistry A, Vol. 115, Issue 9 https://doi.org/10.1021/jp111311k	journal	March 2011
On the Electronic Structures and Electron Affinities of the m -Benzoquinone (BQ) Diradical and the o -, p -BQ Molecules: A Synergetic Photoelectron Spectroscopic and Theoretical Study Fu, Qiang; Yang, Jinlong; Wang, Xue-Bin The Journal of Physical Chemistry A, Vol. 115, Issue 15 https://doi.org/10.1021/jp1120542	journal	April 2011
A computational investigation of the electron affinity of CO3 and the thermodynamic feasibility of CO3-(H2O)n+ROOH reactions Cappa, Christopher D.; Elrod, Matthew J. Physical Chemistry Chemical Physics, Vol. 3, Issue 15 https://doi.org/10.1039/b102981a	journal	January 2001
Untangling the formation of the cyclic carbon trioxide isomer in low temperature carbon dioxide ices Bennett, Chris J.; Jamieson, C.; Mebel, Alexander M. Physical Chemistry Chemical Physics, Vol. 6, Issue 4 https://doi.org/10.1039/b315626p	journal	January 2004
Mechanistical studies on the formation and destruction of carbon monoxide (CO), carbon dioxide (CO2), and carbon trioxide (CO3) in interstellar ice analog samples Bennett, Chris J.; Jamieson, Corey S.; Kaiser, Ralf I. Physical Chemistry Chemical Physics, Vol. 12, Issue 16 https://doi.org/10.1039/b917162b	journal	January 2010
The synergy between qualitative theory, quantitative calculations, and direct experiments in understanding, calculating, and measuring the energy differences between the lowest singlet and triplet states of organic diradicals Carl Lineberger, W.; Thatcher Borden, Weston Physical Chemistry Chemical Physics, Vol. 13, Issue 25 https://doi.org/10.1039/c0cp02786c	journal	January 2011
Elementary processes of photochemical reactions Franck, J.; Dymond, E. G. Transactions of the Faraday Society, Vol. 21, Issue February https://doi.org/10.1039/tf9262100536	journal	January 1926
A detailed study on the symmetry breaking and its effect on the potential surface of NO3 Eisfeld, Wolfgang; Morokuma, Keiji The Journal of Chemical Physics, Vol. 113, Issue 14 https://doi.org/10.1063/1.1290607	journal	October 2000
Geometry and Electronic Structure of Carbon Trioxide Gimarc, B. M.; Chou, T. S. The Journal of Chemical Physics, Vol. 49, Issue 9 https://doi.org/10.1063/1.1670715	journal	November 1968
Infrared Spectrum and Structure of the Species CO ₃ Jacox, Marilyn E.; Milligan, Dolphus E. The Journal of Chemical Physics, Vol. 54, Issue 3 https://doi.org/10.1063/1.1675021	journal	February 1971
Reaction of O( ¹ D ) with CO ₂ at Low Temperatures Weissberger, Edward; Breckenridge, W. H.; Taube, Henry The Journal of Chemical Physics, Vol. 47, Issue 5 https://doi.org/10.1063/1.1712161	journal	September 1967
Carbon Trioxide: Its Production, Infrared Spectrum, and Structure Studied in a Matrix of Solid CO ₂ Moll, Norman G.; Clutter, Dale R.; Thompson, Warren E. The Journal of Chemical Physics, Vol. 45, Issue 12 https://doi.org/10.1063/1.1727526	journal	December 1966
Some Photochemical Reactions of O ₃ in the Gas Phase Katakis, D.; Taube, H. The Journal of Chemical Physics, Vol. 36, Issue 2 https://doi.org/10.1063/1.1732521	journal	January 1962
Development of a low-temperature photoelectron spectroscopy instrument using an electrospray ion source and a cryogenically controlled ion trap Wang, Xue-Bin; Wang, Lai-Sheng Review of Scientific Instruments, Vol. 79, Issue 7 https://doi.org/10.1063/1.2957610	journal	July 2008
Normal coordinate analyses of the neutral CO ₃ and SO ₄ molecules LaBonville, P.; Kugel, R.; Ferraro, J. R. The Journal of Chemical Physics, Vol. 67, Issue 4 https://doi.org/10.1063/1.435022	journal	August 1977
A study of the reaction O−3+CO2?CO−3+O2 and its implication on the thermochemistry of CO3 and O3 and their negative ions Dotan, I.; Davidson, J. A.; Streit, G. E. The Journal of Chemical Physics, Vol. 67, Issue 6 https://doi.org/10.1063/1.435155	journal	January 1977
Photodissociation of negative ions formed in CO ₂ and CO ₂ /O ₂ mixtures Vestal, M. L.; Mauclaire, G. H. The Journal of Chemical Physics, Vol. 67, Issue 8 https://doi.org/10.1063/1.435316	journal	October 1977
Laser photoelectron, photodetachment, and photodestruction spectra of O ⁻ ₃ Novick, Stewart E.; Engelking, Paul C.; Jones, Patrick L. The Journal of Chemical Physics, Vol. 70, Issue 6 https://doi.org/10.1063/1.437842	journal	March 1979
Tandem quadrupole study of laser photodissociation of CO ⁻ ₃ Hiller, J. F.; Vestal, M. L. The Journal of Chemical Physics, Vol. 72, Issue 9 https://doi.org/10.1063/1.439806	journal	May 1980
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples Purvis, George D.; Bartlett, Rodney J. The Journal of Chemical Physics, Vol. 76, Issue 4 https://doi.org/10.1063/1.443164	journal	February 1982
Photodissociation dynamics of CO ₃ ⁻ Hunton, D. E.; Hofmann, M.; Lindeman, T. G. The Journal of Chemical Physics, Vol. 82, Issue 1 https://doi.org/10.1063/1.448786	journal	January 1985
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen Dunning, Thom H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456153	journal	January 1989
Photodissociation of CO ⁻ ₃ : Product kinetic energy measurements as a probe of excited state potential surfaces and dissociation dynamics Snodgrass, Joseph T.; Roehl, Coleen M.; van Koppen, Petra A. M. The Journal of Chemical Physics, Vol. 92, Issue 10 https://doi.org/10.1063/1.458363	journal	May 1990
Second‐order perturbation theory with a complete active space self‐consistent field reference function Andersson, Kerstin; Malmqvist, Per‐Åke; Roos, Björn O. The Journal of Chemical Physics, Vol. 96, Issue 2 https://doi.org/10.1063/1.462209	journal	January 1992
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J. The Journal of Chemical Physics, Vol. 96, Issue 9 https://doi.org/10.1063/1.462569	journal	May 1992
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Pseudo Jahn-Teller coupling in trioxides XO ₃ ^(0,1,−1) with 22 and 23 valence electrons Grein, Friedrich The Journal of Chemical Physics, Vol. 138, Issue 20 https://doi.org/10.1063/1.4805064	journal	May 2013
Ozone and carbon trioxide synthesis by low energy ion implantation onto solid carbon dioxide and implications to astrochemistry Sivaraman, Bhalamurugan; Raja Sekhar, B. N.; Fulvio, Daniele The Journal of Chemical Physics, Vol. 139, Issue 7 https://doi.org/10.1063/1.4818166	journal	August 2013
Stability of polyatomic molecules in degenerate electronic states - I—Orbital degeneracy Jahn, H. A.; Teller, E. Proceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, Vol. 161, Issue 905, p. 220-235 https://doi.org/10.1098/rspa.1937.0142	journal	July 1937
A Theory of Intensity Distribution in Band Systems Condon, Edward Physical Review, Vol. 28, Issue 6 https://doi.org/10.1103/PhysRev.28.1182	journal	December 1926
Photodetachment of thermally relaxed C O 3 − Hong, S. P.; Woo, S. B.; Helmy, E. M. Physical Review A, Vol. 15, Issue 4 https://doi.org/10.1103/PhysRevA.15.1563	journal	April 1977
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Vibrationally Induced Perturbations in Molecular Electron Distributions Bader, Richard F. W. Canadian Journal of Chemistry, Vol. 40, Issue 6 https://doi.org/10.1139/v62-178	journal	June 1962
THE PHOTOLYSIS OF CO ₂ AT 1 470 Å Ung, A. -Y.; Schiff, H. I. Canadian Journal of Chemistry, Vol. 44, Issue 16 https://doi.org/10.1139/v66-295	journal	August 1966

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