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For Rh6D2+, the IRMPD spectrum indicates that one D2 molecule is molecularly adsorbed side-on (\u03b72) to a Rh atom in the octahedral Rh core, although the DFT calculations predict the dissociative adsorption form to be thermodynamically more stable. The energy barrier for the dissociation of D2 on Rh6+ from the molecular adsorption state was calculated to be +0.28 eV, which suggests the kinetic trapping of the molecular adsorption isomer under low-temperature experimental conditions. For Rh6D4+, one D2 molecule is adsorbed molecularly, whereas the other two D atoms are adsorbed separately on bridge sites of the Rh core. For both Rh6D2+ and Rh6D4+ the red-shift of the vibrational wavenumber indicates Kubas bonding, in which the electron density in the bonding \u03c3 orbital of D2 is transferred to the Rh atom forming a shallow potential well. Born-Oppenheimer Molecular Dynamics (BOMD) simulations for Rh6D2+ reproduce the band broadening, which can be explained by the fluctuations of the D\u2013D bond length and the D2 orientation. For Rh6D8+, the Rh core adopts a bicapped tetrahedral structure. For RhnD2+ (n = 5, 7, and 8), the IRMPD spectra show that D2 is dissociatively adsorbed in the dominant isomer. The reaction pathways obtained by DFT calculations demonstrate that the dissociation of D2 on Rh7+ proceeds with a lower energy barrier than that for Rh6+; this explains the different adsorption forms of D2 on Rh6+ and Rh7+.<\/jats:p>","DOI":"10.1021\/acs.jpca.6c04634","type":"journal-article","created":{"date-parts":[[2026,9,12]],"date-time":"2026-09-12T16:02:27Z","timestamp":1789228947000},"page":"7696-7705","source":"Crossref","is-referenced-by-count":0,"title":["Adsorption Forms\nof Hydrogen Molecules on Gas-Phase\nRhodium Cluster Cations Revealed via Messenger-Complex Infrared Multiple\nPhoton Dissociation Spectroscopy"],"prefix":"10.1021","volume":"130","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-3259-8959","authenticated-orcid":true,"given":"Xueshan","family":"Wu","sequence":"first","affiliation":[{"name":"The University of Tokyo , , Komaba , Meguro-ku, ,","place":["Tokyo, Japan, 153-8902"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xirui","family":"Deng","sequence":"additional","affiliation":[{"name":"The University of Tokyo , , Komaba , Meguro-ku, ,","place":["Tokyo, Japan, 153-8902"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2452-3784","authenticated-orcid":true,"given":"Masato","family":"Yamaguchi","sequence":"additional","affiliation":[{"name":"The University of Tokyo , , Komaba , Meguro-ku, ,","place":["Tokyo, Japan, 153-8902"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7118-1628","authenticated-orcid":true,"given":"Satoshi","family":"Kudoh","sequence":"additional","affiliation":[{"name":"The University of Tokyo , , Komaba , Meguro-ku, ,","place":["Tokyo, Japan, 153-8902"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6359-4748","authenticated-orcid":true,"given":"Yufei","family":"Zhang","sequence":"additional","affiliation":[{"name":"The University of Tokyo , , Komaba , Meguro-ku, ,","place":["Tokyo, Japan, 153-8902"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kenichi","family":"Okutsu","sequence":"additional","affiliation":[{"name":"Gakushuin University , , Mejiro, Toshima-ku, ,","place":["Tokyo, Japan, 171-8588"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6239-9289","authenticated-orcid":true,"given":"Jun-ya","family":"Kohno","sequence":"additional","affiliation":[{"name":"Gakushuin University , , Mejiro, Toshima-ku, ,","place":["Tokyo, Japan, 171-8588"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0000-6820-6740","authenticated-orcid":true,"given":"Rutger T.","family":"Zijlstra","sequence":"additional","affiliation":[{"name":"HFML-FELIX , Toernooiveld 7 , ,","place":["Nijmegen, The Netherlands, 6525 ED"]},{"name":"Radboud University, Institute for Molecules and Materials , Heyendaalseweg 135 , ,","place":["Nijmegen, The Netherlands, 6525 AX"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1394-7661","authenticated-orcid":true,"given":"Joost M.","family":"Bakker","sequence":"additional","affiliation":[{"name":"HFML-FELIX , Toernooiveld 7 , ,","place":["Nijmegen, The Netherlands, 6525 ED"]},{"name":"Radboud University, Institute for Molecules and Materials , Heyendaalseweg 135 , ,","place":["Nijmegen, The Netherlands, 6525 AX"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8860-6354","authenticated-orcid":true,"given":"Fumitaka","family":"Mafune\u0301","sequence":"additional","affiliation":[{"name":"The University of Tokyo , , Komaba , Meguro-ku, ,","place":["Tokyo, Japan, 153-8902"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,12]]},"reference":[{"issue":"17","key":"2026092408075082300_cit1","doi-asserted-by":"publisher","first-page":"7368","DOI":"10.1016\/j.ijhydene.2009.05.093","article-title":"Hydrogen\nthe Fuel for 21st Century","volume":"34","author":"Jain","year":"2009","journal-title":"Int. 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