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In this work, the adsorption of methanol on Con+ (n = 1\u201360) clusters is investigated using low-pressure collision cell experiments in combination with time-of-flight mass spectrometry. Experiments are conducted using both methanol and deuterated methanol in order to examine potential isotope effects and to gain insights into the reaction mechanism. Kinetic data and Rice\u2013Ramsperger\u2013Kassel\u2013Marcus calculations indicate the absence of methanol desorption for n &amp;lt; 10 cluster sizes, suggesting dissociative chemisorption of methanol for those sizes. For larger clusters, the reaction involves a combination of association and desorption, with a pronounced size dependence of the corresponding reaction rates. This size dependence is anti-correlated with the promotion energy of an electron from an occupied frontier orbital to the lowest unoccupied d-state.<\/jats:p>","DOI":"10.1063\/5.0247536","type":"journal-article","created":{"date-parts":[[2025,2,18]],"date-time":"2025-02-18T11:23:52Z","timestamp":1739877832000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":1,"title":["Adsorption of methanol on cationic cobalt clusters in the gas phase"],"prefix":"10.1063","volume":"162","author":[{"ORCID":"https:\/\/orcid.org\/0009-0001-4890-2922","authenticated-orcid":false,"given":"Sijie","family":"Yang","sequence":"first","affiliation":[{"name":"MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi\u2019an Jiaotong University 1 , Xi\u2019an 710049,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ya-Ke","family":"Li","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi\u2019an Jiaotong University 1 , Xi\u2019an 710049,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chenchen","family":"Ji","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources School of Chemical Engineering and Technology, Xinjiang University 2 , Urumqi 830017,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6096-7772","authenticated-orcid":false,"given":"Piero","family":"Ferrari","sequence":"additional","affiliation":[{"name":"Quantum Solid-State Physics, Department of Physics and Astronomy, KU Leuven 3 , 3001 Leuven,","place":["Belgium"]},{"name":"Radboud University, Institute of Molecules and Materials, FELIX Laboratory 4 , Toernooiveld 7, 6525 ED Nijmegen,","place":["The Netherlands"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1547-798X","authenticated-orcid":false,"given":"Shengchun","family":"Yang","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi\u2019an Jiaotong University 1 , Xi\u2019an 710049,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5945-1194","authenticated-orcid":false,"given":"Ewald","family":"Janssens","sequence":"additional","affiliation":[{"name":"Quantum Solid-State Physics, Department of Physics and Astronomy, KU Leuven 3 , 3001 Leuven,","place":["Belgium"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1196-2777","authenticated-orcid":false,"given":"Gao-Lei","family":"Hou","sequence":"additional","affiliation":[{"name":"MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi\u2019an Jiaotong University 1 , Xi\u2019an 710049,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2025,2,18]]},"reference":[{"key":"2025021811234591300_c1","volume-title":"Beyond Oil and Gas: The Methanol Economy","year":"2009"},{"key":"2025021811234591300_c2","doi-asserted-by":"publisher","first-page":"1922","DOI":"10.1021\/acscatal.5b00007","article-title":"Methanol to olefins (MTO): From fundamentals to commercialization","volume":"5","year":"2015","journal-title":"ACS Catal."},{"key":"2025021811234591300_c3","doi-asserted-by":"publisher","first-page":"1266","DOI":"10.3390\/membranes12121266","article-title":"Design and utilization of a direct methanol fuel cell","volume":"12","year":"2022","journal-title":"Membranes"},{"key":"2025021811234591300_c4","doi-asserted-by":"publisher","first-page":"8085","DOI":"10.1021\/jp3047196","article-title":"Edge-induced active sites enhance the reactivity of large aluminum cluster anions with alcohols","volume":"116","year":"2012","journal-title":"J.\u00a0Phys. 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