{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,30]],"date-time":"2026-04-30T21:52:06Z","timestamp":1777585926850,"version":"3.51.4"},"reference-count":40,"publisher":"SAGE Publications","issue":"2","license":[{"start":{"date-parts":[[2009,4,1]],"date-time":"2009-04-01T00:00:00Z","timestamp":1238544000000},"content-version":"tdm","delay-in-days":0,"URL":"https:\/\/journals.sagepub.com\/page\/policies\/text-and-data-mining-license"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Eur J Mass Spectrom (Chichester)"],"published-print":{"date-parts":[[2009,4]]},"abstract":"<jats:p>\n                    Threshold photoelectron\u2013photoion coincidence (TPEPICO) spectroscopy has been employed to investigate the competition between bond cleavage and rearrangement reactions in the dissociation of ionized nitromethane, 1. Modeling TPEPICO breakdown diagrams with a combination of RRKM theory and ab initio calculations at the G3 level of theory allowed the derivation of the activation energy for the isomerisation of 1 to ionized methyl nitrite, 2, 82 kJ mol\n                    <jats:sup>\u22121<\/jats:sup>\n                    . In addition, evidence was found for a transition state switch in the bond cleavage reaction in 1 leading to CH\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2022<\/jats:sup>\n                    + NO\n                    <jats:sub>2<\/jats:sub>\n                    <jats:sup>+<\/jats:sup>\n                    . As internal energy increases, the effective transition state for this reaction becomes tighter (i.e. is characterized by a lower entropy of activation, \u0394\n                    <jats:sup>\u2021<\/jats:sup>\n                    S). Fitted thresholds for NO\n                    <jats:sup>+<\/jats:sup>\n                    and CH\n                    <jats:sub>2<\/jats:sub>\n                    OHO\n                    <jats:sup>+<\/jats:sup>\n                    ions, originating from the isomeric methyl nitrite ion, are consistent with G3 level ab initio calculations.\n                  <\/jats:p>","DOI":"10.1255\/ejms.943","type":"journal-article","created":{"date-parts":[[2009,3,19]],"date-time":"2009-03-19T09:56:17Z","timestamp":1237456577000},"page":"157-166","source":"Crossref","is-referenced-by-count":8,"title":["Nitro\u2013Nitrite Isomerization and Transition State Switching in the Dissociation of Ionized Nitromethane: A Threshold Photoelectron\u2013Photoion Coincidence Spectroscopy Study"],"prefix":"10.1177","volume":"15","author":[{"given":"Brandon","family":"Ferrier","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of Ottawa, 10 Marie-Curie, Ottawa, Ontario, Canada K1N 6N5"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Anne-Marie","family":"Boulanger","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Ottawa, 10 Marie-Curie, Ottawa, Ontario, Canada K1N 6N5"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"David M.P.","family":"Holland","sequence":"additional","affiliation":[{"name":"Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"David A.","family":"Shaw","sequence":"additional","affiliation":[{"name":"Daresbury Laboratory, Daresbury, Warrington, Cheshire WA4 4AD UK"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Paul M.","family":"Mayer","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Ottawa, 10 Marie-Curie, Ottawa, Ontario, Canada K1N 6N5"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"179","published-online":{"date-parts":[[2009,10,1]]},"reference":[{"key":"bibr1-ejms.943","doi-asserted-by":"publisher","DOI":"10.1021\/jp971928p"},{"key":"bibr2-ejms.943","doi-asserted-by":"publisher","DOI":"10.1063\/1.1772357"},{"key":"bibr3-ejms.943","doi-asserted-by":"publisher","DOI":"10.1063\/1.1678346"},{"key":"bibr4-ejms.943","doi-asserted-by":"publisher","DOI":"10.1039\/f29757101577"},{"key":"bibr5-ejms.943","doi-asserted-by":"publisher","DOI":"10.1016\/0022-4073(62)90023-7"},{"key":"bibr6-ejms.943","doi-asserted-by":"publisher","DOI":"10.1016\/0375-9601(78)90371-7"},{"key":"bibr7-ejms.943","doi-asserted-by":"publisher","DOI":"10.1246\/cl.1972.903"},{"key":"bibr8-ejms.943","doi-asserted-by":"publisher","DOI":"10.1246\/bcsj.47.2563"},{"key":"bibr9-ejms.943","doi-asserted-by":"publisher","DOI":"10.1016\/0168-1176(88)80104-6"},{"key":"bibr10-ejms.943","doi-asserted-by":"publisher","DOI":"10.1021\/ja01041a026"},{"key":"bibr11-ejms.943","doi-asserted-by":"publisher","DOI":"10.1063\/1.1696898"},{"key":"bibr12-ejms.943","doi-asserted-by":"publisher","DOI":"10.1063\/1.1740568"},{"key":"bibr13-ejms.943","doi-asserted-by":"publisher","DOI":"10.1063\/1.444909"},{"key":"bibr14-ejms.943","first-page":"194","volume":"23","author":"Collin J.","year":"1954","journal-title":"Bull. 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