{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T05:01:11Z","timestamp":1790226071523,"version":"4.1.0"},"reference-count":61,"publisher":"Wiley","license":[{"start":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T00:00:00Z","timestamp":1790121600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T00:00:00Z","timestamp":1790121600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["EXC 2033\u2013390677874"],"award-info":[{"award-number":["EXC 2033\u2013390677874"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["217133147\/SFB 1073"],"award-info":[{"award-number":["217133147\/SFB 1073"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>(LMO) is a versatile and earth\u2010abundant Li intercalation compound of high interest for sustainable energy storage and conversion. Yet, its broader adoption as a cathode in Li\u2010ion batteries or as a water\u2010splitting electrocatalyst is hindered by severe degradation reactions at the solid\u2013electrolyte interface. This instability is rooted in its mixed\u2010valence \/ electronic structure, which is governed by the Li content. Still, the atomistic link between the lithiation state and interfacial degradation remains elusive. Here, we investigate aqueous LMO interfaces across varying lithiation states by atomistic simulations using an ab initio\u2010quality machine learning potential. We demonstrate that the local Li content determines surface Mn oxidation states and reveal their decisive role in interfacial acid\u2013base chemistry. By analyzing the vibrational features of interfacial species, we identify the O\u2013H stretching band as a sensitive spectroscopic probe of the surface electronic structure. Distinct, oxidation\u2010state\u2010dependent shifts reveal a fundamental vulnerability of the mixed\u2010valence spinel surface: the coexistence of Lewis\u2010acidic  centers and oxygen sites neighboring , which are susceptible to electrophilic attack. These findings provide a compelling atomistic rationale extending the conventional \u2010centric view of acid\u2010promoted Mn dissolution toward a dual\u2010site mechanism driven by LMO's mixed\u2010valent\u00a0nature.<\/jats:p>","DOI":"10.1002\/anie.3712910","type":"journal-article","created":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T04:26:02Z","timestamp":1790223962000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Insights into the Degradation Mechanism of Aqueous LiMn\n                    <sub>2<\/sub>\n                    O\n                    <sub>4<\/sub>\n                    \u2013Cathode Interfaces by Computational Vibrational Spectroscopy"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4433-7700","authenticated-orcid":false,"given":"K. Nikolas","family":"Lausch","sequence":"first","affiliation":[{"name":"Lehrstuhl f\u00fcr Theoretische Chemie II Ruhr\u2010Universit\u00e4t Bochum Bochum Germany"},{"name":"Research Center Chemical Sciences and Sustainability Research Alliance Ruhr Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0002-9411-0990","authenticated-orcid":false,"given":"Redouan","family":"El Haouari","sequence":"additional","affiliation":[{"name":"Lehrstuhl f\u00fcr Theoretische Chemie II Ruhr\u2010Universit\u00e4t Bochum Bochum Germany"},{"name":"Research Center Chemical Sciences and Sustainability Research Alliance Ruhr Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2417-1472","authenticated-orcid":false,"given":"Philipp","family":"Schienbein","sequence":"additional","affiliation":[{"name":"Lehrstuhl f\u00fcr Theoretische Chemie II Ruhr\u2010Universit\u00e4t Bochum Bochum Germany"},{"name":"Research Center Chemical Sciences and Sustainability Research Alliance Ruhr Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1220-1542","authenticated-orcid":false,"given":"J\u00f6rg","family":"Behler","sequence":"additional","affiliation":[{"name":"Lehrstuhl f\u00fcr Theoretische Chemie II Ruhr\u2010Universit\u00e4t Bochum Bochum Germany"},{"name":"Research Center Chemical Sciences and Sustainability Research Alliance Ruhr Bochum Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,23]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/0025\u20105408(83)90138\u20101"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010020\u201015355\u20100"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41560\u2010021\u201000815\u20108"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.abc5454"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1038\/s43246\u2010025\u201000733\u20102"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1149\/2.0101614jes"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/0022\u20104596(81)90323\u20106"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1149\/1.2219710"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja3091438"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1149\/1.1836981"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jpowsour.2005.01.043"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jpowsour.2005.08.019"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/cm501125e"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.0c00936"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0021452"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemmater.6b04429"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.98.146401"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/qua.24890"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201703114"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c00868"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41578\u2010021\u201000314\u2010y"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.56.1354"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/eem2.12017"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.95.235150"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.101.205113"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.102.073005"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.102.174102"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0073449"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.8b01288"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41524\u2010021\u201000636\u2010z"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.2110077118"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0016004"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CP01708C"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.3c02001"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.86.4314"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1016\/0013\u20104686(93)80053\u20103"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4944633"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c06717"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0275244"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1630560"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1088\/0965\u20100393\/18\/1\/015012"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1131536"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr040377d"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1039\/b919544k"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.5b00640"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS01059F"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1016\/0167\u20107322(94)00769\u20101"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1088\/0953\u20108984\/24\/12\/124106"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.7b00713"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.5c02395"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.6c00245"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF03354882"},{"key":"e_1_2_7_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr9001879"},{"key":"e_1_2_7_55_1","volume-title":"The Hydrogen Bond and the Water Molecule: The Physics and Chemistry of Water, Aqueous and Bio Media","author":"Mar\u00e9chal Y.","year":"2008"},{"key":"e_1_2_7_56_1","doi-asserted-by":"publisher","DOI":"10.1016\/0010\u20104655(95)00053\u2010I"},{"key":"e_1_2_7_57_1","volume-title":"Molecular Modelling: Principles and Applications","author":"Leach A. 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N.Lausch R.El Haouari P.Schienbein andJ.Behler \u201cSupporting Data for: Insights into the Degradation Mechanism of Aqueous LiMn2O4\u2010Cathode Interfaces by Computational Vibrational Spectroscopy \u201dTUDOdata V1 https:\/\/doi.org\/10.17877\/RESOLV\u20102026\u2010MTVHVF8D."}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.3712910","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.3712910","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.3712910","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,24]],"date-time":"2026-09-24T04:26:05Z","timestamp":1790223965000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.3712910"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,23]]},"references-count":61,"alternative-id":["10.1002\/anie.3712910"],"URL":"https:\/\/doi.org\/10.1002\/anie.3712910","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,23]]},"assertion":[{"value":"2026-04-07","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-04","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-23","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e3712910"}}