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Upon excitation to the S<jats:sub>2<\/jats:sub> state of Z, the internal conversion to the S<jats:sub>1<\/jats:sub> state would be dominant. From the S<jats:sub>1<\/jats:sub> state, two intersystem crossing paths leading to the T<jats:sub>2<\/jats:sub> and T<jats:sub>1<\/jats:sub> states and one internal conversion path to the S<jats:sub>0<\/jats:sub> state are possible. However, considering the large barrier to access the S<jats:sub>1<\/jats:sub>\/S<jats:sub>0<\/jats:sub> conical intersection and the strong spin\u2010orbit coupling between S<jats:sub>1<\/jats:sub> and T<jats:sub>2<\/jats:sub> states (&gt;40\u2009cm<jats:sup>\u22121<\/jats:sup>), the intersystem crossing to the triplet manifolds is predicted to be more preferred. Arriving at the T<jats:sub>2<\/jats:sub> state, the internal conversion to the T<jats:sub>1<\/jats:sub> state and the intersystem crossing back to the S<jats:sub>1<\/jats:sub> state are both possible considering the S<jats:sub>1<\/jats:sub>\/T<jats:sub>2<\/jats:sub>\/T<jats:sub>1<\/jats:sub> three\u2010state intersection near the T<jats:sub>2<\/jats:sub> minimum. Upon arrival at the T<jats:sub>1<\/jats:sub> state, the deactivation to S<jats:sub>0<\/jats:sub> can be efficient after overcoming a small barrier to access T<jats:sub>1<\/jats:sub>\/S<jats:sub>0<\/jats:sub> crossing point, where the spin\u2010orbit coupling (SOC) is as large as 39.7\u2009cm<jats:sup>\u22121<\/jats:sup>. Our present work not only provides in\u2010depth insights into the photoinduced process of unnatural base Z, but can also help the future design of novel unnatural bases with better photostability.<\/jats:p>","DOI":"10.1111\/php.13884","type":"journal-article","created":{"date-parts":[[2023,12,2]],"date-time":"2023-12-02T17:00:43Z","timestamp":1701536443000},"page":"380-392","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":7,"title":["Theoretical insights into the photophysics of an unnatural base Z: A <scp>MS\u2010CASPT2<\/scp> investigation"],"prefix":"10.1111","volume":"100","author":[{"given":"Xin\u2010Rui","family":"Chen","sequence":"first","affiliation":[{"name":"College of Chemistry and Material Science Sichuan Normal University  Chengdu China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Wen\u2010Jun","family":"Jiang","sequence":"additional","affiliation":[{"name":"College of Chemistry and Material 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