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The threshold photoelectron spectra of both compounds are featureless and lack a definitive origin transition, owing to the internal rotation of the formate functional group relative to the benzene ring, active upon ionisation. CBS\u2010QB3 calculations yield ionisation energies of 8.88 and 9.03\u2009eV for PF and PCF, respectively. Ionised PF dissociates by the loss of CO via a transition state composed of a phenoxy cation and HCO moieties. The dissociation of PCF ions involves the competing losses of CO (<jats:italic>m<\/jats:italic>\/<jats:italic>z<\/jats:italic> 128\/130), Cl (<jats:italic>m<\/jats:italic>\/<jats:italic>z<\/jats:italic> 121) and CO<jats:sub>2<\/jats:sub> (<jats:italic>m<\/jats:italic>\/<jats:italic>z<\/jats:italic> 112\/114), with Cl loss also shown to occur from the second excited state in a non\u2010statistical process. The primary CO\u2010 and Cl\u2010loss fragment ions undergo sequential reactions leading to fragment ions at <jats:italic>m<\/jats:italic>\/<jats:italic>z<\/jats:italic> 98 and 77. The mass\u2010analysed ion kinetic energy (MIKE) spectrum of PCF<jats:sup>+<\/jats:sup> showed that the loss of CO<jats:sub>2<\/jats:sub> occurs with a large reverse energy barrier, which is consistent with the computationally derived minimum energy reaction pathway.<\/jats:p>","DOI":"10.1002\/jms.5004","type":"journal-article","created":{"date-parts":[[2024,2,4]],"date-time":"2024-02-04T21:49:22Z","timestamp":1707083362000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["What a difference a chlorine makes: The remarkable unimolecular ion chemistry of phenyl formate and phenyl chloroformate"],"prefix":"10.1002","volume":"59","author":[{"given":"Bethany","family":"Lowe","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biomolecular Sciences University of Ottawa  Ottawa Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4790-4579","authenticated-orcid":false,"given":"Alejandro L.","family":"Cardona","sequence":"additional","affiliation":[{"name":"INFIQC \u2013 CONICET, Departamento fisicoqu\u00edmica, Universidad Nacional de C\u00f3rdoba  C\u00f3rdoba Argentina"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Juana","family":"Salas","sequence":"additional","affiliation":[{"name":"INFIQC \u2013 CONICET, Departamento fisicoqu\u00edmica, Universidad Nacional de C\u00f3rdoba  C\u00f3rdoba Argentina"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2742-1051","authenticated-orcid":false,"given":"Andras","family":"Bodi","sequence":"additional","affiliation":[{"name":"Laboratory for Synchrotron Radiation and Femtochemistry Paul Scherrer Institute  Villigen Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6112-4398","authenticated-orcid":false,"given":"Paul M.","family":"Mayer","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biomolecular Sciences University of Ottawa  Ottawa Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2002-7481","authenticated-orcid":false,"given":"Maxi A.","family":"Burgos Paci","sequence":"additional","affiliation":[{"name":"INFIQC \u2013 CONICET, Departamento fisicoqu\u00edmica, Universidad Nacional de C\u00f3rdoba  C\u00f3rdoba Argentina"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2024,2,4]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.3390\/catal13020224"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CC09413A"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.combustflame.2019.10.002"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/0020\u20107381(78)80057\u20106"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2013.06.026"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201403441"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/kin.20939"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4742769"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/B978\u20100\u201012\u2010409547\u20102.11311\u20103"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1593788"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/b915400k"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp3091705"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100004a042"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1002\/oms.1210220904"},{"key":"e_1_2_7_16_1","unstructured":"FrischMJ TrucksGW SchlegelHB et al.Gaussian 16 rev. 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