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This study aims to understand the mechanism of TMP unimolecular thermal decomposition to support the integration of a TMP chemical kinetic model into a LIB electrolyte surrogate model. Reactive intermediates and products of TMP thermal decomposition were experimentally detected using vacuum ultraviolet (VUV) synchrotron radiation and double imaging photoelectron photoion coincidence (<jats:italic>i<\/jats:italic><jats:sup>2<\/jats:sup>PEPICO) spectroscopy. Phosphorus\u2010containing intermediates such as PO, HPO and HPO<jats:sub>2<\/jats:sub> were identified. Sampling effects could successfully be obviated thanks to photoion imaging, which also showed evidence for isomerization reactions upon wall collisions in the ionization chamber. Quantum chemical calculations performed for the unimolecular decomposition of TMP revealed for the first time that isomerization channels via hydrogen and methyl transfer (barrier heights of 65.9 and 72.6\u2005kcal\/mol, respectively) are the lowest\u2010energy primary steps of TMP decomposition followed by CH<jats:sub>3<\/jats:sub>OH\/CH<jats:sub>3<\/jats:sub>\/CH<jats:sub>2<\/jats:sub>O or dimethyl ether (DME) production, respectively. We found an analogous DME production channel in the unimolecular decomposition of dimethyl methylphosphonate (DMMP), another important OPC fire\u2010retardant additive with a similar molecular structure to TMP, which are not included in currently available chemical kinetic models.<\/jats:p>","DOI":"10.1002\/chem.202401750","type":"journal-article","created":{"date-parts":[[2024,6,15]],"date-time":"2024-06-15T05:03:25Z","timestamp":1718427805000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":16,"title":["The Unimolecular Decomposition Mechanism of Trimethyl Phosphate"],"prefix":"10.1002","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0529-1006","authenticated-orcid":false,"given":"Keisuke","family":"Kanayama","sequence":"first","affiliation":[{"name":"Laboratory for Synchrotron Radiation and Femtochemistry Paul Scherrer Institute  CH 5232 Villigen PSI Switzerland"},{"name":"Institute of Fluid Science Tohoku 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