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The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide |
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| Authors: | Xianxu Chu Weiyu Qian Bo Lu Dr. Lina Wang Jie Qin Prof. Dr. Jun Li Prof. Dr. Guntram Rauhut Dr. Tarek Trabelsi Prof. Dr. Joseph S. Francisco Prof. Dr. Xiaoqing Zeng |
| Affiliation: | 1. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123 China;2. Department of Chemistry, Fudan University, Shanghai, 200433 China;3. School of Chemistry and Chemical Engineering and Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University, Chongqing, 401331 China;4. Institute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany;5. Department of Earth and Environment Science and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania, 19104-6243 USA |
| Abstract: | Phosphorus monoxide (.PO) is a key intermediate in phosphorus chemistry, and its association with the hydroxyl radical (.OH) to yield metaphosphorous acid (cis-HOPO) contributes to the chemiluminescence in the combustion of phosphines. When photolyzing cis-HOPO in an Ar-matrix at 2.8 K, the simplest dioxophosphorane HPO2 and an elusive hydroxyl radical complex (HRC) of .PO form. This prototypical radical-radical complex reforms into cis-HOPO at above 12.0 K by overcoming a barrier of 0.28±0.02 kcal mol−1. The vibrational spectra of this HRC and its D- and 18O-isotopologues suggest a structure of .OH⋅⋅⋅OP., for which a triplet spin multiplicity with a binding energy of −3.20 kcal mol−1 has been computed at the UCCSD(T)-F12a/aug-cc-pVTZ level. |
| Keywords: | complexes hydrogen bonds IR spectroscopy phosphorus oxides radicals |