{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,11]],"date-time":"2026-09-11T15:47:02Z","timestamp":1789141622469,"version":"build-2803163510"},"reference-count":81,"publisher":"Wiley","issue":"21","license":[{"start":{"date-parts":[[2021,9,7]],"date-time":"2021-09-07T00:00:00Z","timestamp":1630972800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2021,11,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Studying the effects of UV and VUV radiation on non\u2010canonical DNA\/RNA nucleobases allows us to compare how they release excess energy following absorption with respect to their canonical counterparts. This has attracted much research attention in recent years because of its likely influence on the origin of our genetic lexicon in prebiotic times. Here we present a CASSCF and XMS\u2010CASPT2 theoretical study of the photoionisation of non\u2010canonical pyrimidine nucleobase isocytosine in both its keto and enol tautomeric forms. We analyse their lowest energy cationic excited states including <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/cphc202100402-math-0001.png\" xlink:title=\"urn:x-wiley:14394235:media:cphc202100402:cphc202100402-math-0001\"\/>\n, <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/cphc202100402-math-0002.png\" xlink:title=\"urn:x-wiley:14394235:media:cphc202100402:cphc202100402-math-0002\"\/>\n and <jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/cphc202100402-math-0003.png\" xlink:title=\"urn:x-wiley:14394235:media:cphc202100402:cphc202100402-math-0003\"\/>\n and compare these to the corresponding electronic states in cytosine. Investigating lower\u2010energy decay pathways we find \u2013 unexpectedly \u2010 that keto\u2010isocytosine<jats:sup>+<\/jats:sup> presents a sizeable energy barrier potentially inhibiting decay to its cationic ground state, whereas enol\u2010isocytosine<jats:sup>+<\/jats:sup> features a barrierless and consequently ultrafast pathway analogous to the one previously found for the canonical (keto) form of cytosine<jats:sup>+<\/jats:sup>. Dynamic electron correlation reduces the energy barrier in the keto form substantially (by \u223c1\u2005eV) but it is nevertheless still present. We additionally compute the UV\/Vis absorption signals of the structures encountered along these decay channels to provide spectroscopic fingerprints to assist future experiments in monitoring these intricate photo\u2010processes.<\/jats:p>","DOI":"10.1002\/cphc.202100402","type":"journal-article","created":{"date-parts":[[2021,8,9]],"date-time":"2021-08-09T15:11:15Z","timestamp":1628521875000},"page":"2172-2181","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Modelling Photoionisation in Isocytosine: Potential Formation of Longer\u2010Lived Excited State Cations in its Keto Form"],"prefix":"10.1002","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2076-3406","authenticated-orcid":false,"given":"Javier","family":"Segarra\u2010Mart\u00ed","sequence":"first","affiliation":[{"name":"Department of Chemistry Molecular Sciences Research Hub Imperial College London  White City Campus, 82 Wood Lane London W12 0BZ UK"},{"name":"Present address: Instituto de Ciencia Molecular Universitat de Valencia  P.O. Box 22085 ES-46071 Valencia Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1117-7536","authenticated-orcid":false,"given":"Michael J.","family":"Bearpark","sequence":"additional","affiliation":[{"name":"Department of Chemistry Molecular Sciences Research Hub Imperial College London  White City Campus, 82 Wood Lane London W12 0BZ UK"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,9,7]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0206770"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1146\/annurev.physchem.59.032607.093719"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz101122t"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00444"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms1893"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp408073d"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1109\/JSTQE.2011.2107892"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3586812"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.86.053406"},{"key":"e_1_2_8_10_1","first-page":"021010","volume":"1","author":"Kotur M.","year":"2011","journal-title":"Phys. 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