{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T17:09:19Z","timestamp":1788887359482,"version":"build-2803163510"},"reference-count":54,"publisher":"MDPI AG","issue":"18","license":[{"start":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T00:00:00Z","timestamp":1788825600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"The Natural Science Foundation of Jiangsu Province","award":["BK20150118"],"award-info":[{"award-number":["BK20150118"]}]},{"name":"the Natural Science Foundation of Wuxi Institute of Technology","award":["ZK202104"],"award-info":[{"award-number":["ZK202104"]}]},{"award":["ZK202104"],"award-info":[{"award-number":["ZK202104"]}],"id":[{"id":"https:\/\/ror.org\/00ab95029","id-type":"ROR","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["11905084"],"award-info":[{"award-number":["11905084"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"award":["11905084"],"award-info":[{"award-number":["11905084"]}],"id":[{"id":"https:\/\/ror.org\/01h0zpd94","id-type":"ROR","asserted-by":"publisher"}]},{"name":"Colleges and Universities in Jiangsu Province Natural Science Research Projects","award":["20KJB140002"],"award-info":[{"award-number":["20KJB140002"]}]},{"name":"Jiangsu University\u2019s \u201cQing Lan Project\u201d"},{"id":[{"id":"https:\/\/ror.org\/03jc41j30","id-type":"ROR","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Understanding the activation mechanism of water molecules is of fundamental importance for catalytic water dissociation via water splitting. In this study, we employed first-principles molecular dynamics simulations to investigate the catalytic dissociation of H2O on 88 alloy clusters. Our results reveal that a larger red shift in the center of the coupled \u03bd1 and \u03bd3 stretching modes of adsorbed H2O correlates with a lower dissociation temperature. We observe an empirical correlation suggesting that dissociation is facilitated when the adsorption energy is comparable in magnitude to the HOMO\u2013LUMO gap, which we propose as a hypothesis warranting further investigation with excited-state methods. Furthermore, comparison of the frontier molecular orbitals between precursor and intermediate states demonstrates that the number of frontier orbitals exhibiting increased overlap with the dissociating H atom is inversely correlated with the dissociation temperature. These findings provide atomic-scale insights into the activation mechanism of water dissociation on isolated gas-phase clusters and establish spectroscopic descriptors for evaluating the intrinsic reactivity of such model systems. We caution that extension of these findings to practical catalytic water splitting would require consideration of additional factors such as catalyst supports, solvents, and realistic reaction conditions.<\/jats:p>","DOI":"10.3390\/molecules31183165","type":"journal-article","created":{"date-parts":[[2026,9,8]],"date-time":"2026-09-08T16:46:04Z","timestamp":1788885964000},"page":"3165","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Correlations Between Vibrational Red Shifts, Electronic Structure, and Water Dissociation on Alloy Clusters: An Exploratory Computational Study"],"prefix":"10.3390","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5870-4965","authenticated-orcid":false,"given":"Yanbiao","family":"Wang","sequence":"first","affiliation":[{"name":"Department of Fundamental Courses, Wuxi University of Technology, Wuxi 214121, China"},{"name":"Department of Physics, Southeast University, Nanjing 211189, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"methodology","vocabulary":"credit"}]},{"given":"Xinglong","family":"Pan","sequence":"additional","affiliation":[{"name":"School of Mechanical Technology, Wuxi University of Technology, Wuxi 214121, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"software","vocabulary":"credit"}]},{"given":"Tingting","family":"Liu","sequence":"additional","affiliation":[{"name":"Department of Fundamental Courses, Wuxi University of Technology, Wuxi 214121, China"}],"role":[{"vocabulary":"crossref","role":"author"},{"role":"validation","vocabulary":"credit"}]}],"member":"1968","published-online":{"date-parts":[[2026,9,8]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1903120","DOI":"10.1002\/aenm.201903120","article-title":"Recent advances on water-splitting electrocatalysis mediated by noble-metal-based nanostructured materials","volume":"10","author":"Li","year":"2020","journal-title":"Adv. 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