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We use fixed-node diffusion Monte Carlo (FN-DMC) to investigate three principal decomposition pathways: dehydration, C\u2013C bond cleavage, and H2 elimination. The obtained results are compared with those from Hartree\u2013Fock (HF), hybrid density functional theory (B3LYP), modified Gaussian-2 composite theory, and experimental kinetic data. By recovering the missing many-body correlation, FN-DMC lowers the HF forward activation barriers by 4\u201315\u00a0kcal mol\u22121 and yields barrier heights that are consistent with available Arrhenius activation parameters within expected thermal corrections. A correlation-energy analysis along the intrinsic reaction coordinate reveals a pathway-dependent modulation of dynamical correlation near the transition state, with the largest stabilization observed for the dehydration channel. The results demonstrate that FN-DMC provides a robust description of static activation barriers and offers mechanistic insight into the evolution of electron-correlation effects in complex bond-breaking reactions.<\/jats:p>","DOI":"10.1063\/5.0315750","type":"journal-article","created":{"date-parts":[[2026,3,2]],"date-time":"2026-03-02T12:03:07Z","timestamp":1772452987000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Quantifying electron correlation effects in ethanol decomposition pathways"],"prefix":"10.1063","volume":"164","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6635-5061","authenticated-orcid":false,"given":"L.","family":"C\u00e2ndido","sequence":"first","affiliation":[{"name":"Instituto de F\u00edsica, Universidade Federal de Goi\u00e1s 1 , 74001-970 Goi\u00e2nia, GO,","place":["Brazil"]},{"name":"Instituto de F\u00edsica de S\u00e3o Carlos, Universidade de S\u00e3o Paulo 2 , 13560-970 S\u00e3o Carlos, SP,","place":["Brazil"]}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6734-7971","authenticated-orcid":false,"given":"G.-Q.","family":"Hai","sequence":"additional","affiliation":[{"name":"Instituto de F\u00edsica de S\u00e3o Carlos, Universidade de S\u00e3o Paulo 2 , 13560-970 S\u00e3o Carlos, SP,","place":["Brazil"]}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"317","published-online":{"date-parts":[[2026,3,2]]},"reference":[{"key":"2026030207030035400_c1","doi-asserted-by":"publisher","first-page":"9505","DOI":"10.1021\/ie401157c","volume":"52","year":"2013","journal-title":"Ind. 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