Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX – (E = As, P, and N; X = S and O) Anions
Journal Article
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· Journal of the American Chemical Society
- Physical Sciences Division, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States
- Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States
- Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
- Department of Chemistry and Applied Biology, ETH-Hönggerberg, 8093 Zürich, Switzerland
- Department of Chemistry: Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany
- Department of Chemistry and the Center for Advanced Scientific Computing and Modeling, University of North Texas, 1155 Union Circle, #305070, Denton, Texas 76203-5017, United States
Three newly-synthesized [Na+(221-kryptofix)] salts containing AsCO–, PCO–, and PCS– anions were successfully electrosprayed into the vacuum, and the ECX– (E = As, P; X = O, S) anions were investigated by negative ion photoelectron spectroscopy (NIPES) and high resolution photoelectron imaging spectroscopy. For each ECX– anion, a well-resolved NIPE spectrum was obtained, in which every major peak is split into a doublet. The splittings are attributed to spin-orbit coupling (SOC) in the ECX• radicals. Vibrational progressions in the NIPE spectra of ECX– were assigned to the symmetric and antisymmetric stretching modes in ECX• radicals. The electron affinities (EAs) and SOC splittings of ECX• are determined from the NIPE spectra to be: AsCO•: EA = 2.414 ± 0.002 eV, SOC splitting = 988 cm-1; PCO•: EA = 2.670 ± 0.005 eV, SOC splitting = 175 cm-1; PCS•: EA = 2.850 ± 0.005 eV, SOC splitting = 300 cm-1. Calculations using the B3LYP, CASPT2, and CCSD(T) methods all predict linear geometries for both the anions and neutral radicals. The calculated EAs and SOC splittings for ECX• are in excellent agreement with the experimentally-measured values. The simulated NIPE spectra, based on the calculated Franck-Condon factors, and SOC splittings nicely reproduce all of the observed spectral peaks, thus allowing unambiguous spectral assignments. The finding that PCS has the greatest EA of the three triatomic molecules considered here is counterintuitive based upon electronegativity considerations, but understandable in terms of the HOMO of PCS– having the greatest degree of delocalization onto both terminal atoms.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1390425
- Report Number(s):
- PNNL-SA-124942; 48584; KC0301050
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 26 Vol. 139; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
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OSTI ID:1577106
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OSTI ID:1560282
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Tue Sep 03 20:00:00 EDT 2019
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