{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,10]],"date-time":"2026-09-10T15:15:31Z","timestamp":1789053331415,"version":"build-2803163510"},"reference-count":50,"publisher":"Wiley","issue":"47","license":[{"start":{"date-parts":[[2020,7,28]],"date-time":"2020-07-28T00:00:00Z","timestamp":1595894400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2020,8,21]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Reactive species, such as\n                    <jats:sup>.<\/jats:sup>\n                    PO\n                    <jats:sub>2<\/jats:sub>\n                    and HOPO, are considered of upmost importance in flame inhibition and catalytic combustion processes of fuels. However, the underlying chemistry of their formation remains speculative due to the unavailability of suitable analytical techniques that can be used to identify the transient species which lead to their formation. This study elucidates the reaction mechanisms of the formation of phosphoryl species from dimethyl methyl phosphonate (DMMP) and dimethyl methyl phosphoramidate (DMPR) under well\u2010defined oxidative conditions. Photoelectron photoion coincidence techniques that utilized vacuum ultraviolet synchrotron radiation were applied to isomer\u2010selectively detect the elusive key intermediates and stable products. With the help of in situ recorded spectral fingerprints, different transient species, such as PO\n                    <jats:sub>2<\/jats:sub>\n                    and triplet O radicals, have been exclusively identified from their isomeric components, which has helped to piece together the formation mechanisms of phosphoryl species under various conditions. It was found that\n                    <jats:sup>.<\/jats:sup>\n                    PO\n                    <jats:sub>2<\/jats:sub>\n                    formation required oxidative conditions above 1070\u2005K. The combined presence of O\n                    <jats:sub>2<\/jats:sub>\n                    and H\n                    <jats:sub>2<\/jats:sub>\n                    led to significant changes in the decomposition chemistry of both model phosphorus compounds, leading to the formation of\n                    <jats:sup>.<\/jats:sup>\n                    PO\n                    <jats:sub>2<\/jats:sub>\n                    . The reaction\n                    <jats:sup>.<\/jats:sup>\n                    PO+O\n                    <jats:sub>2<\/jats:sub>\n                    \u2192\n                    <jats:sup>.<\/jats:sup>\n                    PO\n                    <jats:sub>2<\/jats:sub>\n                    +O: was identified as the key step in the formation of\n                    <jats:sup>.<\/jats:sup>\n                    PO\n                    <jats:sub>2<\/jats:sub>\n                    . Interestingly, the presence of O\n                    <jats:sub>2<\/jats:sub>\n                    in DMPR thermolysis suppresses the formation of PN\u2010containing species. In a previous study, PN species were identified as the major species formed during the pyrolysis of DMPR. Thus, the findings of this study has shed light onto the decomposition pathways of organophosphorus compounds, which are beneficial for their fuel additive and fire suppressant applications.\n                  <\/jats:p>","DOI":"10.1002\/chem.202001388","type":"journal-article","created":{"date-parts":[[2020,5,20]],"date-time":"2020-05-20T16:02:08Z","timestamp":1589990528000},"page":"10795-10800","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":31,"title":["The Underlying Chemistry to the Formation of PO\n                    <sub>2<\/sub>\n                    Radicals from Organophosphorus Compounds: A Missing Puzzle Piece in Flame Chemistry"],"prefix":"10.1002","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7773-8236","authenticated-orcid":false,"given":"Shuyu","family":"Liang","sequence":"first","affiliation":[{"name":"Laboratory of Inorganic Chemistry ETH Z\u00fcrich, Swiss Federal Institute of Technology  Vladimir-Prelog-Weg 1\u20135\/10 Z\u00fcrich Switzerland"},{"name":"Additives and Chemistry, Advanced Fibers Empa, Swiss Federal Laboratories for Materials Science  Lerchenfeldstrasse 5 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1251-4549","authenticated-orcid":false,"given":"Patrick","family":"Hemberger","sequence":"additional","affiliation":[{"name":"Laboratory for Synchrotron Radiation and Femtochemistry Paul Scherrer Institute  WSLA\/115 Villigen-PSI Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8206-6588","authenticated-orcid":false,"given":"Mathias","family":"Steglich","sequence":"additional","affiliation":[{"name":"Laboratory for Synchrotron Radiation and Femtochemistry Paul Scherrer Institute  WSLA\/115 Villigen-PSI Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pietro","family":"Simonetti","sequence":"additional","affiliation":[{"name":"Additives and Chemistry, Advanced Fibers Empa, Swiss Federal Laboratories for Materials Science  Lerchenfeldstrasse 5 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3146-0176","authenticated-orcid":false,"given":"Jo\u00eblle","family":"Levalois\u2010Gr\u00fctzmacher","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry ETH Z\u00fcrich, Swiss Federal Institute of Technology  Vladimir-Prelog-Weg 1\u20135\/10 Z\u00fcrich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1531-8906","authenticated-orcid":false,"given":"Hansj\u00f6rg","family":"Gr\u00fctzmacher","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry ETH Z\u00fcrich, Swiss Federal Institute of Technology  Vladimir-Prelog-Weg 1\u20135\/10 Z\u00fcrich Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9891-5249","authenticated-orcid":false,"given":"Sabyasachi","family":"Gaan","sequence":"additional","affiliation":[{"name":"Additives and Chemistry, Advanced Fibers Empa, Swiss Federal Laboratories for Materials Science  Lerchenfeldstrasse 5 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,7,28]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201711735"},{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201711735"},{"key":"e_1_2_7_2_1","unstructured":"\u00a0"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-2180(94)00224-G"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-2180(93)90022-U"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-2180(93)90118-M"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b02420"},{"key":"e_1_2_7_7_1","unstructured":"\u00a0"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.combustflame.2005.08.011"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1080\/713713013"},{"key":"e_1_2_7_10_1","unstructured":"\u00a0"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.proci.2018.06.140"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1134\/S0010508211010023"},{"key":"e_1_2_7_13_1","unstructured":"\u00a0"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.polymdegradstab.2008.06.010"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-2180(98)00101-1"},{"key":"e_1_2_7_16_1","unstructured":"\u00a0"},{"key":"e_1_2_7_17_2","first-page":"751","volume-title":"Numerical Simulations of Gas-Phase Interactions of Phosphorus-Containing Compounds with Cup-Burner Flames","author":"Takahashi F.","year":"2017"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1080\/13647830.2015.1115556"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0082-0784(00)80576-7"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201404271"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201700402"},{"key":"e_1_2_7_22_1","unstructured":"\u00a0"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4CP02857K"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.4861175"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp5036579"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CP02964C"},{"key":"e_1_2_7_27_1","unstructured":"\u00a0"},{"key":"e_1_2_7_28_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms15946"},{"key":"e_1_2_7_29_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-018-0071-z"},{"key":"e_1_2_7_30_1","unstructured":"\u00a0"},{"key":"e_1_2_7_31_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-2180(99)00030-9"},{"key":"e_1_2_7_32_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-2180(99)00171-6"},{"key":"e_1_2_7_33_1","unstructured":"\u00a0"},{"key":"e_1_2_7_34_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.3082016"},{"key":"e_1_2_7_35_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.nima.2009.08.069"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4984304"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4965428"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp2068073"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1080\/0144235X.2014.967951"},{"key":"e_1_2_7_40_1","volume-title":"Imaging in Molecular Dynamics","year":"2003"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.2776012"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1593788"},{"key":"e_1_2_7_43_1","unstructured":"Gaussian 09 Revision B.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman G. Scalmani V. Barone B. Mennucci G.\u2005A. Petersson H. Nakatsuji M. Caricato X. Li H.\u2005P. Hratchian A.\u2005F. Izmaylov J. Bloino G. Zheng J.\u2005L. Sonnenberg M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai T. Vreven J.\u2005A. Montgomery J.\u2005E. Peralta F. Ogliaro M. Bearpark J.\u2005J. Heyd E. Brothers K.\u2005N. Kudin V.\u2005N. Staroverov R. Kobayashi J. Normand K. Raghavachari A. Rendell J.\u2005C. Burant S.\u2005S. Iyengar J. Tomasi M. Cossi N. Rega J.\u2005M. Millam M. Klene J.\u2005E. Knox J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski R.\u2005L. Martin K. Morokuma V.\u2005G. Zakrzewski G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg S. Dapprich A.\u2005D. Daniels Farkas J.\u2005B. Foresman J.\u2005V. Ortiz J. Cioslowski D.\u2005J. Fox Wallingford CT 2009."},{"key":"e_1_2_7_44_1","unstructured":"\u00a0"},{"key":"e_1_2_7_45_2","unstructured":"A. Mozhayskiy A.\u2005I. Krylov ezSpectrumhttp:\/\/iopenshell.usc.edu\/downloads 2014;"},{"key":"e_1_2_7_46_2","unstructured":"C.\u2005M. Western PGOPHER a Program for Simulating Rotational Structure http:\/\/pgopher.chm.bris.ac.uk University of Bristol."},{"key":"e_1_2_7_47_1","unstructured":"\u00a0"},{"key":"e_1_2_7_48_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.477924"},{"key":"e_1_2_7_49_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.481224"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.202001388","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202001388","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.202001388","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202001388","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T09:40:31Z","timestamp":1760262031000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202001388"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,7,28]]},"references-count":50,"journal-issue":{"issue":"47","published-print":{"date-parts":[[2020,8,21]]}},"alternative-id":["10.1002\/chem.202001388"],"URL":"https:\/\/doi.org\/10.1002\/chem.202001388","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,7,28]]},"assertion":[{"value":"2020-03-20","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2020-07-28","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}