Infrared spectrum and intermolecular potential energy surface of the CO-O 2 dimer
Only a few weakly-bound complexes containing the O2 molecule have been characterized by high resolution spectroscopy, no doubt due to the complications added by the oxygen molecule's unpaired electron spin. Here we report an extensive infrared spectrum of CO-O2, observed in the CO fundamental b...
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Published in | Physical chemistry chemical physics : PCCP Vol. 20; no. 21; pp. 14431 - 14440 |
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Main Authors | , , , , , |
Format | Journal Article |
Language | English |
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07.06.2018
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Abstract | Only a few weakly-bound complexes containing the O2 molecule have been characterized by high resolution spectroscopy, no doubt due to the complications added by the oxygen molecule's unpaired electron spin. Here we report an extensive infrared spectrum of CO-O2, observed in the CO fundamental band region using a tunable quantum cascade laser to probe a pulsed supersonic jet expansion. The rotational energy level pattern derived from the spectrum consists of stacks of levels characterized by the total angular momentum, J, and its projection on the intermolecular axis, K. Five such stacks are observed in the ground vibrational state, and ten in the excited state (ν(CO) = 1). They are divided into two groups, with no observed transitions between groups. The groups correspond to different projections of the O2 electron spin, and correlate with the two lowest fine structure states of O2, (N, J) = (1, 0) and (1, 2). The rotational constant of the lowest K = 0 stack implies an effective intermolecular separation of 3.82 Å, but this should be interpreted with caution since it ignores possible effects of electron spin. A new high-level 4-dimensional potential energy surface is developed for CO-O2, and rotational energy levels are calculated for this surface, ignoring electron spin. By comparing calculated and observed levels, it is possible to assign detailed quantum labels to the observed level stacks. |
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AbstractList | Only a few weakly-bound complexes containing the O2 molecule have been characterized by high resolution spectroscopy, no doubt due to the complications added by the oxygen molecule's unpaired electron spin. Here we report an extensive infrared spectrum of CO-O2, observed in the CO fundamental band region using a tunable quantum cascade laser to probe a pulsed supersonic jet expansion. The rotational energy level pattern derived from the spectrum consists of stacks of levels characterized by the total angular momentum, J, and its projection on the intermolecular axis, K. Five such stacks are observed in the ground vibrational state, and ten in the excited state (ν(CO) = 1). They are divided into two groups, with no observed transitions between groups. The groups correspond to different projections of the O2 electron spin, and correlate with the two lowest fine structure states of O2, (N, J) = (1, 0) and (1, 2). The rotational constant of the lowest K = 0 stack implies an effective intermolecular separation of 3.82 Å, but this should be interpreted with caution since it ignores possible effects of electron spin. A new high-level 4-dimensional potential energy surface is developed for CO-O2, and rotational energy levels are calculated for this surface, ignoring electron spin. By comparing calculated and observed levels, it is possible to assign detailed quantum labels to the observed level stacks. Only a few weakly-bound complexes containing the O 2 molecule have been characterized by high resolution spectroscopy, no doubt due to the complications added by the oxygen molecule's unpaired electron spin. Here we report an extensive infrared spectrum of CO–O 2 , observed in the CO fundamental band region using a tunable quantum cascade laser to probe a pulsed supersonic jet expansion. The rotational energy level pattern derived from the spectrum consists of stacks of levels characterized by the total angular momentum, J , and its projection on the intermolecular axis, K . Five such stacks are observed in the ground vibrational state, and ten in the excited state ( ν (CO) = 1). They are divided into two groups, with no observed transitions between groups. The groups correspond to different projections of the O 2 electron spin, and correlate with the two lowest fine structure states of O 2 , ( N , J ) = (1, 0) and (1, 2). The rotational constant of the lowest K = 0 stack implies an effective intermolecular separation of 3.82 Å, but this should be interpreted with caution since it ignores possible effects of electron spin. A new high-level 4-dimensional potential energy surface is developed for CO–O 2 , and rotational energy levels are calculated for this surface, ignoring electron spin. By comparing calculated and observed levels, it is possible to assign detailed quantum labels to the observed level stacks. |
Author | Dawes, Richard Barclay, A J Wang, Xiao-Gang McKellar, A R W Carrington, Tucker Moazzen-Ahmadi, N |
Author_xml | – sequence: 1 givenname: A J surname: Barclay fullname: Barclay, A J email: nmoazzen@ucalgary.ca organization: Department of Physics and Astronomy, University of Calgary, 2500 University Drive North West, Calgary, Alberta T2N 1N4, Canada. nmoazzen@ucalgary.ca – sequence: 2 givenname: A R W surname: McKellar fullname: McKellar, A R W organization: National Research Council of Canada, Ottawa, Ontario K1A 0R6, Canada – sequence: 3 givenname: N orcidid: 0000-0001-8307-3480 surname: Moazzen-Ahmadi fullname: Moazzen-Ahmadi, N email: nmoazzen@ucalgary.ca organization: Department of Physics and Astronomy, University of Calgary, 2500 University Drive North West, Calgary, Alberta T2N 1N4, Canada. nmoazzen@ucalgary.ca – sequence: 4 givenname: Richard surname: Dawes fullname: Dawes, Richard organization: Department of Chemistry, Missouri University of Science and Technology, Rolla, MO 65409-0010, USA – sequence: 5 givenname: Xiao-Gang surname: Wang fullname: Wang, Xiao-Gang organization: Chemistry Department, Queen's University, Kingston, Ontario K7L 3N6, Canada – sequence: 6 givenname: Tucker orcidid: 0000-0002-5200-2353 surname: Carrington fullname: Carrington, Tucker organization: Chemistry Department, Queen's University, Kingston, Ontario K7L 3N6, Canada |
BackLink | https://www.ncbi.nlm.nih.gov/pubmed/29781029$$D View this record in MEDLINE/PubMed |
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CitedBy_id | crossref_primary_10_1080_00268976_2021_1980234 crossref_primary_10_1021_acs_jcim_8b00784 crossref_primary_10_1093_mnras_stab2563 crossref_primary_10_1039_D2CP04101D crossref_primary_10_1146_annurev_physchem_090519_051837 crossref_primary_10_1093_mnras_staa3821 crossref_primary_10_1039_D0CP04186F crossref_primary_10_1039_C9CP01044K |
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Snippet | Only a few weakly-bound complexes containing the O2 molecule have been characterized by high resolution spectroscopy, no doubt due to the complications added... Only a few weakly-bound complexes containing the O 2 molecule have been characterized by high resolution spectroscopy, no doubt due to the complications added... |
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Title | Infrared spectrum and intermolecular potential energy surface of the CO-O 2 dimer |
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