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Previous time-dependent density functional theory (TDDFT) calculations suggested two distinct crossing regions between S0 and S1, but the corresponding S0\u2013S1 energy gaps are too large to enable an efficient nonadiabatic S0 \u2192 S1 transition. In this work, we employ state-of-the-art multireference wave function theory (WFT), the density matrix renormalization group (DMRG) method, employing large active spaces comprising up to 36 orbitals, to elucidate the excited-state generation pathway. By providing a more accurate description of strong electron correlation in the biradical regime, our DMRG-based potential energy profile resolves the crossing topology into a single S0\/S1 near-degenerate region, with the energy gap reduced by nearly an order of magnitude. This mechanistic picture is further supported by good agreement between computed and experimental emission wavelengths, as well as a Landau\u2013Zener model analysis that predicts a high nonadiabatic transition probability.<\/jats:p>","DOI":"10.1021\/acs.jpclett.6c02533","type":"journal-article","created":{"date-parts":[[2026,9,21]],"date-time":"2026-09-21T20:03:05Z","timestamp":1790020985000},"page":"11252-11260","source":"Crossref","is-referenced-by-count":0,"title":["Resolving the S0\/S1 Crossing\nTopology for the Excited-State Origin of\n                    <i>Watasenia scintillans<\/i>\n                    Bioluminescence"],"prefix":"10.1021","volume":"17","author":[{"given":"Cheng","family":"Peng","sequence":"first","affiliation":[{"name":"Shandong University , , 72 Binhai Road , ,","place":["Qingdao, China, 266237"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shuangqi","family":"Pi","sequence":"additional","affiliation":[{"name":"Beijing Normal University , , ,","place":["Zhuhai, China, 519087"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8761-5339","authenticated-orcid":true,"given":"Ya-Jun","family":"Liu","sequence":"additional","affiliation":[{"name":"Beijing Normal University , , ,","place":["Zhuhai, China, 519087"]},{"name":"Beijing Normal University , , ,","place":["Beijing, China, 100875"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7915-3429","authenticated-orcid":true,"given":"Haibo","family":"Ma","sequence":"additional","affiliation":[{"name":"Shandong University , , 72 Binhai Road , ,","place":["Qingdao, China, 266237"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,21]]},"reference":[{"key":"2026100109090543700_cit1","doi-asserted-by":"publisher","first-page":"189","DOI":"10.1016\/S0005-2736(02)00447-9","article-title":"Bioluminescence\nreaction catalyzed by membrane-bound luciferase in the \u201cfirefly\nsquid,\u201d Watasenia scintillans","volume":"1564","author":"Tsuji","year":"2002","journal-title":"Biochimica\net Biophysica Acta (BBA) - Biomembranes"},{"key":"2026100109090543700_cit2","doi-asserted-by":"publisher","first-page":"250","DOI":"10.1016\/j.bbrc.2005.08.215","article-title":"Role of\nmolecular oxygen in the bioluminescence of the firefly squid, Watasenia\nscintillans","volume":"338","author":"Tsuji","year":"2005","journal-title":"Biochem. 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