{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T12:04:28Z","timestamp":1789646668035,"version":"4.0.0"},"reference-count":41,"publisher":"MDPI AG","issue":"18","license":[{"start":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T00:00:00Z","timestamp":1789603200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"2025 Second Batch Scientific Research Startup Fund Project for High-Level Talents of Chengdu Aeronautic Polytechnic University","award":["ZZX0625170"],"award-info":[{"award-number":["ZZX0625170"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Alkylcyclohexanes are vital components of aviation kerosene. Intramolecular H\u2212migration of \u2022OOQOOH radicals controls ketohydroperoxide (KHP) formation, the primary pathway responsible for low-temperature chain-branching during low\u2212temperature oxidation. Available chemical kinetic models for alkylcyclohexanes generally lack directly computed kinetic data for H\u2212migration reactions of \u2022OOQOOH in cyclic fuels; relevant rate constants are commonly transferred from analogous alkane reactions, introducing systematic uncertainties in low\u2212temperature ignition predictions. In this work, quantum chemical calculations are performed for 13 representative \u2022OOQOOH intramolecular H\u2212migration pathways originating from alkylcyclohexanes, covering six structural subclasses: 1,5\u2212H\u2212(s)(p), 1,5\u2212H\u2212(s)(s), 1,5\u2212H\u2212(t)(p), 1,5\u2212H\u2212(t)(s), 1,6\u2212H\u2212(t)(p), and 1,6\u2212H\u2212(t)(s). Modified Arrhenius parameters are fitted from high\u2212pressure\u2212limit rate constants over 500\u20131500 K. Further comparison between the present computed rate data and parameters adopted in existing mechanisms demonstrates that the literature values transferred from alkanes are systematically lower. Ring strain and distinct transition\u2212state entropy originating from cyclic structures make the alkane kinetic parameters inappropriate for alkylcyclohexane systems. The kinetic parameters and lumped subclass rate rules obtained in this study provide fundamental data for improving low-temperature oxidation models of alkylcyclohexanes.<\/jats:p>","DOI":"10.3390\/molecules31183299","type":"journal-article","created":{"date-parts":[[2026,9,17]],"date-time":"2026-09-17T11:41:35Z","timestamp":1789645295000},"page":"3299","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Intramolecular H\u2212Migration Kinetics of \u2022OOQOOH Radicals for KHP Formation During Low-Temperature Oxidation of Alkylcyclohexanes"],"prefix":"10.3390","volume":"31","author":[{"given":"Xiaoxia","family":"Yao","sequence":"first","affiliation":[{"name":"Aviation Maintenance Industry College, Chengdu Aeronautic Polytechnic University, Chengdu 610100, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"investigation","vocabulary":"credit"},{"role":"resources","vocabulary":"credit"},{"role":"data-curation","vocabulary":"credit"},{"role":"writing-original-draft","vocabulary":"credit"},{"role":"visualization","vocabulary":"credit"},{"role":"project-administration","vocabulary":"credit"},{"role":"funding-acquisition","vocabulary":"credit"}]},{"given":"Yuheng","family":"Liu","sequence":"additional","affiliation":[{"name":"Aviation Maintenance Industry College, Chengdu Aeronautic Polytechnic University, Chengdu 610100, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"investigation","vocabulary":"credit"},{"role":"methodology","vocabulary":"credit"}]},{"given":"Ying","family":"Xuan","sequence":"additional","affiliation":[{"name":"Aviation Maintenance Industry College, Chengdu Aeronautic Polytechnic University, Chengdu 610100, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"investigation","vocabulary":"credit"},{"role":"data-curation","vocabulary":"credit"}]},{"given":"Junjiang","family":"Guo","sequence":"additional","affiliation":[{"name":"School of Chemical Engineering, Guizhou Institute of Technology, Guiyang 550003, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"investigation","vocabulary":"credit"},{"role":"writing-review-editing","vocabulary":"credit"}]},{"given":"Mingxia","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Physics and New Energy, Chongqing University of Technology, Chongqing 401135, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"investigation","vocabulary":"credit"}]},{"given":"Zerong","family":"Li","sequence":"additional","affiliation":[{"name":"College of Chemistry, Sichuan University, Chengdu 610064, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"investigation","vocabulary":"credit"},{"role":"writing-review-editing","vocabulary":"credit"}]},{"given":"Wenjiong","family":"Hai","sequence":"additional","affiliation":[{"name":"Aviation Maintenance Industry College, Chengdu Aeronautic Polytechnic University, Chengdu 610100, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"investigation","vocabulary":"credit"},{"role":"supervision","vocabulary":"credit"}]}],"member":"1968","published-online":{"date-parts":[[2026,9,17]]},"reference":[{"key":"ref_1","first-page":"20240458","article-title":"Theoretical Study of the Effect of Conformational Structures on the Secondary Oxidation Reactions of cis-1,3-Dimethylcyclohexane","volume":"46","author":"Shen","year":"2025","journal-title":"Chem. 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