{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T13:48:02Z","timestamp":1790689682009,"version":"4.1.0"},"reference-count":29,"publisher":"AIP Publishing","issue":"4","license":[{"start":{"date-parts":[[2023,1,27]],"date-time":"2023-01-27T00:00:00Z","timestamp":1674777600000},"content-version":"am","delay-in-days":365,"URL":"https:\/\/publishing.aip.org\/authors\/rights-and-permissions"}],"funder":[{"DOI":"10.13039\/100006234","name":"Sandia National Laboratories","doi-asserted-by":"publisher","award":["DE-NA0003525"],"award-info":[{"award-number":["DE-NA0003525"]}],"id":[{"id":"10.13039\/100006234","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2022,1,28]]},"abstract":"<jats:p>Understanding hydrogen incorporation into palladium requires detailed knowledge of surface and subsurface structure and atomic interactions as surface hydrogen is being embedded. Using density functional theory (DFT), we examine the energies of hydrogen layers of varying coverage adsorbed on Pd(111). We find that H\u2013H and H\u2013Pd interactions promote the formation of the well-known 3\u00d73 phases but also favor an unreported (3 \u00d7 3) phase at high H coverages for which we present experimental evidence. We relate the stability of isolated H vacancies of the (3 \u00d7 3) phase to the need of H2 molecules to access bare Pd before they can dissociate. Following higher hydrogen dosage, we observe initial steps of hydride formation, starting with small clusters of subsurface hydrogen. The interaction between H and Pd is complicated by the persistent presence of carbon at the surface. X-ray photoelectron spectroscopy experiments show that trace amounts of carbon, emerging from the Pd bulk despite many surface cleaning cycles, become mobile enough to repopulate the C-depleted surface at temperatures above 200\u00a0K. When exposed to hydrogen, these surface carbon atoms react to form benzene, as evidenced by scanning tunneling microscopy observations interpreted with DFT.<\/jats:p>","DOI":"10.1063\/5.0068291","type":"journal-article","created":{"date-parts":[[2022,1,27]],"date-time":"2022-01-27T12:04:16Z","timestamp":1643285056000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":9,"title":["The role of H\u2013H interactions and impurities on the structure and energetics of H\/Pd(111)"],"prefix":"10.1063","volume":"156","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3078-7372","authenticated-orcid":false,"given":"K.","family":"Th\u00fcrmer","sequence":"first","affiliation":[{"name":"Sandia National Laboratories , Livermore, California 94550, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4444-3500","authenticated-orcid":false,"given":"N. C.","family":"Bartelt","sequence":"additional","affiliation":[{"name":"Sandia National Laboratories , Livermore, California 94550, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"J. A.","family":"Whaley","sequence":"additional","affiliation":[{"name":"Sandia National Laboratories , Livermore, California 94550, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"A. H.","family":"McDaniel","sequence":"additional","affiliation":[{"name":"Sandia National Laboratories , Livermore, California 94550, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5822-9938","authenticated-orcid":false,"given":"F.","family":"El Gabaly","sequence":"additional","affiliation":[{"name":"Sandia National Laboratories , Livermore, California 94550, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2022,1,27]]},"reference":[{"key":"2023081000343882800_c1","doi-asserted-by":"publisher","first-page":"269","DOI":"10.1146\/annurev.ms.21.080191.001413","article-title":"The palladium-hydrogen system","volume":"21","year":"1991","journal-title":"Annu. Rev. Mater. Sci."},{"key":"2023081000343882800_c2","doi-asserted-by":"publisher","first-page":"409","DOI":"10.1016\/0021-9517(87)90189-8","article-title":"Studies of isotopic exchange between gaseous-hydrogen and palladium hydride powder","volume":"108","year":"1987","journal-title":"J. Catal."},{"key":"2023081000343882800_c3","doi-asserted-by":"publisher","first-page":"474","DOI":"10.1016\/j.ces.2014.09.001","article-title":"Effects of surface thermodynamics on hydrogen isotope exchange kinetics in palladium: Particle and flow models","volume":"122","year":"2015","journal-title":"Chem. Eng. Sci."},{"key":"2023081000343882800_c4","doi-asserted-by":"publisher","first-page":"705","DOI":"10.1038\/nature01557","article-title":"Dissociative hydrogen adsorption on palladium requires aggregates of three or more vacancies","volume":"422","year":"2003","journal-title":"Nature"},{"key":"2023081000343882800_c5","doi-asserted-by":"publisher","first-page":"L379","DOI":"10.1016\/0039-6028(86)90548-0","article-title":"Order-disorder transitions and subsurface occupation for hydrogen on Pd(111)","volume":"171","year":"1986","journal-title":"Surf. Sci."},{"key":"2023081000343882800_c6","doi-asserted-by":"publisher","first-page":"5","DOI":"10.1016\/s0039-6028(03)00822-7","article-title":"Hydrogen adsorption and diffusion on Pd(111)","volume":"540","year":"2003","journal-title":"Surf. Sci."},{"key":"2023081000343882800_c7","doi-asserted-by":"publisher","first-page":"746","DOI":"10.1002\/bbpc.19720760809","article-title":"Phase-transitions of hydrogen in metals due to elastic interaction","volume":"76","year":"1972","journal-title":"Ber. Bunsen-Ges. Phys. Chem."},{"key":"2023081000343882800_c8","doi-asserted-by":"publisher","first-page":"587","DOI":"10.1080\/00018737400101401","article-title":"Elastic interaction and phase-transition in coherent metal-hydrogen systems","volume":"23","year":"1974","journal-title":"Adv. Phys."},{"key":"2023081000343882800_c9","doi-asserted-by":"publisher","first-page":"434","DOI":"10.1103\/physrevlett.74.434","article-title":"Surface-confined alloy formation in immiscible systems","volume":"74","year":"1995","journal-title":"Phys. Rev. Lett."},{"key":"2023081000343882800_c10","doi-asserted-by":"publisher","first-page":"15","DOI":"10.1016\/0927-0256(96)00008-0","article-title":"Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set","volume":"6","year":"1996","journal-title":"Comput. Mater. Sci."},{"key":"2023081000343882800_c11","doi-asserted-by":"publisher","first-page":"11169","DOI":"10.1103\/physrevb.54.11169","article-title":"Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set","volume":"54","year":"1996","journal-title":"Phys. Rev. B"},{"key":"2023081000343882800_c12","doi-asserted-by":"publisher","first-page":"3865","DOI":"10.1103\/physrevlett.77.3865","article-title":"Generalized gradient approximation made simple","volume":"77","year":"1996","journal-title":"Phys. Rev. Lett."},{"key":"2023081000343882800_c13","doi-asserted-by":"publisher","first-page":"1758","DOI":"10.1103\/physrevb.59.1758","article-title":"From ultrasoft pseudopotentials to the projector augmented-wave method","volume":"59","year":"1999","journal-title":"Phys. Rev. B"},{"issue":"4","key":"2023081000343882800_c14","doi-asserted-by":"publisher","first-page":"146103","DOI":"10.1103\/PhysRevLett.93.146103","article-title":"When Langmuir is too simple: H2 dissociation on Pd(111) at high coverage","volume":"93","year":"2004","journal-title":"Phys. Rev. Lett."},{"key":"2023081000343882800_c15","doi-asserted-by":"publisher","first-page":"10927","DOI":"10.1063\/1.1420732","article-title":"Subsurface impurities in Pd(111) studied by scanning tunneling microscopy","volume":"115","year":"2001","journal-title":"J. Chem. Phys."},{"key":"2023081000343882800_c16","doi-asserted-by":"publisher","first-page":"17907","DOI":"10.1073\/pnas.0506657102","article-title":"Observation and manipulation of subsurface hydride in Pd{111} and its effect on surface chemical, physical, and electronic properties","volume":"102","year":"2005","journal-title":"Proc. Natl. Acad. Sci. U. S. A."},{"key":"2023081000343882800_c17","doi-asserted-by":"publisher","first-page":"5757","DOI":"10.1002\/anie.200604498","article-title":"Manipulation and patterning of the surface hydrogen concentration on Pd(111) by electric fields","volume":"46","year":"2007","journal-title":"Angew. Chem., Int. Ed."},{"key":"2023081000343882800_c18","doi-asserted-by":"publisher","first-page":"154704","DOI":"10.1063\/1.4917537","article-title":"Diffusion of hydrogen interstitials in the near-surface region of Pd(111) under the influence of surface coverage and external static electric fields","volume":"142","year":"2015","journal-title":"J. Chem. Phys."},{"key":"2023081000343882800_c19","doi-asserted-by":"publisher","first-page":"4864","DOI":"10.1007\/s10853-019-04179-z","article-title":"Coherent phase decomposition in the Pd\u2013H system","volume":"55","year":"2020","journal-title":"J. Mater. Sci."},{"issue":"16","key":"2023081000343882800_c20","doi-asserted-by":"publisher","first-page":"165425","DOI":"10.1103\/physrevb.104.165425","article-title":"Structure and energetics of the elbows in the Au(111) herringbone reconstruction","volume":"104","year":"2021","journal-title":"Phys. Rev. B"},{"key":"2023081000343882800_c21","doi-asserted-by":"publisher","first-page":"435","DOI":"10.1016\/0039-6028(74)90060-0","article-title":"Adsorption of hydrogen on palladium single-crystal surfaces","volume":"41","year":"1974","journal-title":"Surf. Sci."},{"key":"2023081000343882800_c22","doi-asserted-by":"publisher","first-page":"8064","DOI":"10.1103\/physrevb.54.8064","article-title":"Separation of the sp3 and sp2 components in the C1s photoemission spectra of amorphous carbon films","volume":"54","year":"1996","journal-title":"Phys. Rev. B"},{"key":"2023081000343882800_c23","doi-asserted-by":"publisher","first-page":"1713","DOI":"10.1016\/j.carbon.2004.03.005","article-title":"XPS photoemission in carbonaceous materials: A \u2018defect\u2019 peak beside the graphitic asymmetric peak","volume":"42","year":"2004","journal-title":"Carbon"},{"key":"2023081000343882800_c24","doi-asserted-by":"publisher","first-page":"10853","DOI":"10.1063\/1.1619942","article-title":"Ultrahigh vacuum and high-pressure coadsorption of CO and H2 on Pd(111): A combined SFG, TDS, and LEED study","volume":"119","year":"2003","journal-title":"J. Chem. Phys."},{"key":"2023081000343882800_c25","doi-asserted-by":"publisher","first-page":"87","DOI":"10.1021\/jz201455s","article-title":"CO-assisted subsurface hydrogen trapping in Pd(111) films","volume":"3","year":"2012","journal-title":"J. Phys. Chem. Lett."},{"key":"2023081000343882800_c26","doi-asserted-by":"publisher","first-page":"356","DOI":"10.1021\/jp013000+","article-title":"Vibrational sum frequency spectroscopy on Pd(111) and supported Pd nanoparticles: CO adsorption from ultrahigh vacuum to atmospheric pressure","volume":"106","year":"2002","journal-title":"J. Phys. Chem. B"},{"key":"2023081000343882800_c27","doi-asserted-by":"publisher","first-page":"337","DOI":"10.1016\/0304-5102(91)85070-i","article-title":"The bonding, structure and reactions of CO2 adsorbed on clean and promoted metal surfaces","volume":"65","year":"1991","journal-title":"J. Mol. Catal."},{"key":"2023081000343882800_c28","doi-asserted-by":"publisher","first-page":"4743","DOI":"10.1002\/anie.200904688","article-title":"Hydrogen diffusion into palladium nanoparticles: Pivotal promotion by carbon","volume":"49","year":"2010","journal-title":"Angew. Chem., Int. Ed."},{"key":"2023081000343882800_c29","doi-asserted-by":"publisher","first-page":"5653","DOI":"10.1021\/jp0373503","article-title":"Chemisorption of benzene on Pt(111), Pd(111), and Rh(111) metal surfaces: A structural and vibrational comparison from first principles","volume":"108","year":"2004","journal-title":"J. Phys. Chem. B"}],"container-title":["The Journal of Chemical Physics"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/aip.scitation.org\/doi\/am-pdf\/10.1063\/5.0068291","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0068291\/16537728\/044707_1_online.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.aip.org\/aip\/jcp\/article-pdf\/doi\/10.1063\/5.0068291\/16537728\/044707_1_online.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,10]],"date-time":"2023-08-10T00:37:33Z","timestamp":1691627853000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.aip.org\/jcp\/article\/156\/4\/044707\/2840801\/The-role-of-H-H-interactions-and-impurities-on-the"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,1,27]]},"references-count":29,"journal-issue":{"issue":"4","published-print":{"date-parts":[[2022,1,28]]}},"URL":"https:\/\/doi.org\/10.1063\/5.0068291","relation":{},"ISSN":["0021-9606","1089-7690"],"issn-type":[{"value":"0021-9606","type":"print"},{"value":"1089-7690","type":"electronic"}],"subject":[],"published-other":{"date-parts":[[2022,1,28]]},"published":{"date-parts":[[2022,1,27]]},"article-number":"044707"}}