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The electronic rearrangements, which describe the mechanism of oxetane formation via carbon\u2010oxygen attack (C\u2212O), comprises of the electronic activation of formaldehyde and accumulation of pairing density on the O once the reaction system is approaching the conical intersection point. Our theoretical evidence based on the ELF topology shows that the C\u2212O bond is formed in the ground\u2010state surface (via C\u2212O attack) returning from the S<jats:sub>1<\/jats:sub> surface accompanied by 1,4\u2010singlet diradical formation. Subsequently, the reaction center is fully activated near the transition state (TS), and the ring\u2010closure (yielding oxetane) involves the C\u2212C bond formation after the TS. For the carbon\u2010carbon attack (C\u2212C), both reactants (formaldehyde and ethylene) are activated, leading to C\u2212C bond formation in the S<jats:sub>1<\/jats:sub> excited state before reaching the conical intersection region. Finally, the C\u2212O formation occurs in the ground\u2010state surface, resulting from the pair density flowing primarily from the C to O atom.<\/jats:p>","DOI":"10.1002\/cphc.202100594","type":"journal-article","created":{"date-parts":[[2021,9,22]],"date-time":"2021-09-22T00:02:08Z","timestamp":1632268928000},"page":"2342-2351","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["Unraveling the Bonding Nature Along the Photochemically Activated Paterno\u2010B\u00fcchi Reaction Mechanism"],"prefix":"10.1002","volume":"22","author":[{"given":"Cristian","family":"Guerra","sequence":"first","affiliation":[{"name":"Universidad Andr\u00e9s Bello Facultad de Ciencias Exactas Departamento de Ciencias Qu\u00edmicas  Avenida, Rep\u00fablica 275 8370146 Santiago de Chile Chile"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Leandro","family":"Ayarde\u2010Henr\u00edquez","sequence":"additional","affiliation":[{"name":"Universidad Andr\u00e9s Bello Facultad de Ciencias Exactas Departamento de Ciencias Qu\u00edmicas  Avenida, Rep\u00fablica 275 8370146 Santiago de Chile Chile"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mario","family":"Duque\u2010Nore\u00f1a","sequence":"additional","affiliation":[{"name":"Universidad Andr\u00e9s Bello Facultad de Ciencias Exactas Departamento de Ciencias Qu\u00edmicas  Avenida, Rep\u00fablica 275 8370146 Santiago de Chile Chile"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9200-9859","authenticated-orcid":false,"given":"Eduardo","family":"Chamorro","sequence":"additional","affiliation":[{"name":"Universidad Andr\u00e9s Bello Facultad de Ciencias Exactas Departamento de Ciencias Qu\u00edmicas  Avenida, Rep\u00fablica 275 8370146 Santiago de Chile Chile"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2021,9,28]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cp40819h"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/c9pp00148d"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol0514496"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/D1RA00033K"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotochemrev.2017.10.002"},{"key":"e_1_2_7_6_1","first-page":"6255","volume":"103","author":"Freilich S. 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