title: Elucidating the thermal decomposition of dimethyl methylphosphonate by vacuum ultraviolet (VUV) photoionization: pathways to the PO radical, a key species in flame-retardant mechanisms.
abstract: The production of phosphoryl species (PO, PO2, HOPO) is believed to be of great importance for efficient flame-retardant action in the gas phase. We present a detailed investigation of the thermal decomposition of dimethyl methylphosphonate (DMMP) probed by vacuum ultraviolet (VUV) synchrotron radiation and imaging photoelectron photoion coincidence (iPEPICO) spectroscopy. This technique provides a snapshot of the thermolysis process and direct evidence of how the reactive phosphoryl species are generated during heat exposure. One of the key findings of this work is that only PO is formed in high concentration upon DMMP decomposition, whereas PO2 is absent. It can be concluded that the formation of PO2 needs an oxidative environment, which is typically the case in a real flame. Based on the identification of products such as methanol, formaldehyde, and PO, as well as the intermediates O=P-CH3, H2C=P-OH, and H2C=P(=O)H, supported by quantum chemical calculations, we were able to describe the predominant pathways that lead to active phosphoryl species during the thermal decomposition of DMMP.
authors.affiliation: Additives and Chemistry, Advanced Fibers, Empa, Swiss Federal Laboratories for Materials Science, Lerchenfeldstrasse 5, 9014 St. Gallen (Switzerland); Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich (Switzerland).
authors.forename: Shuyu
authors.initials: S
authors.lastname: Liang
authors.forename: Patrick
authors.initials: P
authors.lastname: Hemberger
authors.forename: N Matthias
authors.initials: NM
authors.lastname: Neisius
authors.forename: Andras
authors.initials: A
authors.lastname: Bodi
authors.forename: Hansjörg
authors.initials: H
authors.lastname: Grützmacher
authors.forename: Joelle
authors.initials: J
authors.lastname: Levalois-Grützmacher
authors.forename: Sabyasachi
authors.initials: S
authors.lastname: Gaan
keywords: ab initio calculations; organophosphorus compounds; photoelectron spectroscopy; radicals; thermochemistry