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High-level coupled-cluster single, double, triple\/complete basis set energetics were incorporated along minimum-energy paths computed at the MP2\/aug-cc-pVDZ level to provide a consistent description of barrier profiles and reaction exothermicities. Representative systems were further analyzed using microcanonical multidimensional tunneling, while small-curvature tunneling treatments were applied to the remaining reactions. The results reveal that the reactions proceed through an asynchronous oxygen-insertion transition region in which hydrogen transfer and O\u2013O bond weakening occur simultaneously, leading to narrow effective barrier regions and pronounced tunneling sensitivity. For CH2OO + CH4, tunneling enhances the canonical rate constant by nearly two orders of magnitude at 200\u00a0K, and deuterium substitution yields kinetic isotope effects exceeding one order of magnitude at low temperature. Oxygen-isotope effects approaching two at 200\u00a0K further indicate significant heavy-atom tunneling contributions. These reactions provide well-defined theoretical benchmark systems for evaluating tunneling and reaction-path effects in which hydrogen and oxygen tunneling jointly influence rate behavior. Halogen substitution substantially lowers the insertion barrier by up to 16 kcal\/mol and produces rate constants approaching those of benchmark hydrogen-abstraction reactions, suggesting that faster halogenated systems may offer more accessible conditions for future experimental validation. These findings highlight the importance of reaction-path curvature and multidimensional tunneling effects in oxygen-insertion reactions and demonstrate that multidimensional tunneling treatments are essential for reliable kinetic predictions.<\/jats:p>","DOI":"10.1063\/5.0315481","type":"journal-article","created":{"date-parts":[[2026,3,18]],"date-time":"2026-03-18T10:39:15Z","timestamp":1773830355000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Multidimensional tunneling and reaction-path dynamics in oxygen-insertion reactions of Criegee intermediates with small alkanes"],"prefix":"10.1063","volume":"164","author":[{"given":"Kuan-Yi","family":"Chou","sequence":"first","affiliation":[{"name":"Department of Chemistry and Biochemistry, National Chung Cheng University , Chia-Yi 62102,","place":["Taiwan"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-6496-8684","authenticated-orcid":false,"given":"Yi-Wen","family":"Chen","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, National Chung Cheng University , Chia-Yi 62102,","place":["Taiwan"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yu-Ting","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, National Chung Cheng University , Chia-Yi 62102,","place":["Taiwan"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9404-9988","authenticated-orcid":false,"given":"Wei-Ping","family":"Hu","sequence":"additional","affiliation":[{"name":"Department of Chemistry and Biochemistry, National Chung Cheng University , Chia-Yi 62102,","place":["Taiwan"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2026,3,18]]},"reference":[{"key":"2026031806390582700_c1","doi-asserted-by":"publisher","first-page":"745","DOI":"10.1002\/anie.197507451","article-title":"Mechanism of ozonolysis","volume":"14","year":"1975","journal-title":"Angew. 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