{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T22:21:47Z","timestamp":1787005307008,"version":"build-2736575974"},"reference-count":62,"publisher":"AIP Publishing","issue":"7","funder":[{"DOI":"10.13039\/100015539","name":"The Australian Government","doi-asserted-by":"crossref","id":[{"id":"10.13039\/100015539","id-type":"DOI","asserted-by":"crossref"}]},{"DOI":"10.13039\/501100001774","name":"The University of Sydney","doi-asserted-by":"crossref","award":["2012-00076"],"award-info":[{"award-number":["2012-00076"]}],"id":[{"id":"10.13039\/501100001774","id-type":"DOI","asserted-by":"crossref"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2015,8,21]]},"abstract":"<jats:p>Quantum and anharmonic effects are investigated in (H2)2\u2013Li+\u2013benzene, a model for hydrogen adsorption in metal-organic frameworks and carbon-based materials, using rigid-body diffusion Monte Carlo (RBDMC) simulations. The potential-energy surface (PES) is calculated as a modified Shepard interpolation of M05-2X\/6-311+G(2df,p) electronic structure data. The RBDMC simulations yield zero-point energies (ZPE) and probability density histograms that describe the ground-state nuclear wavefunction. Binding a second H2 molecule to the H2\u2013Li+\u2013benzene complex increases the ZPE of the system by 5.6 kJ mol\u22121 to 17.6 kJ mol\u22121. This ZPE is 42% of the total electronic binding energy of (H2)2\u2013Li+\u2013benzene and cannot be neglected. Our best estimate of the 0 K binding enthalpy of the second H2 to H2\u2013Li+\u2013benzene is 7.7 kJ mol\u22121, compared to 12.4 kJ mol\u22121 for the first H2 molecule. Anharmonicity is found to be even more important when a second (and subsequent) H2 molecule is adsorbed; use of harmonic ZPEs results in significant error in the 0 K binding enthalpy. Probability density histograms reveal that the two H2 molecules are found at larger distance from the Li+ ion and are more confined in the \u03b8 coordinate than in H2\u2013Li+\u2013benzene. They also show that both H2 molecules are delocalized in the azimuthal coordinate, \u03d5. That is, adding a second H2 molecule is insufficient to localize the wavefunction in \u03d5. Two fragment-based (H2)2\u2013Li+\u2013benzene PESs are developed. These use a modified Shepard interpolation for the Li+\u2013benzene and H2\u2013Li+\u2013benzene fragments, and either modified Shepard interpolation or a cubic spline to model the H2\u2013H2 interaction. Because of the neglect of three-body H2, H2, Li+ terms, both fragment PESs lead to overbinding of the second H2 molecule by 1.5 kJ mol\u22121. Probability density histograms, however, indicate that the wavefunctions for the two H2 molecules are effectively identical on the \u201cfull\u201d and fragment PESs. This suggests that the 1.5 kJ mol\u22121 error is systematic over the regions of configuration space explored by our simulations. Notwithstanding this, modified Shepard interpolation of the weak H2\u2013H2 interaction is problematic and we obtain more accurate results, at considerably lower computational cost, using a cubic spline interpolation. Indeed, the ZPE of the fragment-with-spline PES is identical, within error, to the ZPE of the full PES. This fragmentation scheme therefore provides an accurate and inexpensive method to study higher hydrogen loading in this and similar systems.<\/jats:p>","DOI":"10.1063\/1.4928760","type":"journal-article","created":{"date-parts":[[2015,8,25]],"date-time":"2015-08-25T14:47:28Z","timestamp":1440514048000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":7,"title":["\u201cPlug-and-Play\u201d potentials: Investigating quantum effects in (H2)2\u2013Li+\u2013benzene"],"prefix":"10.1063","volume":"143","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3309-064X","authenticated-orcid":false,"given":"Jordan H.","family":"D\u2019Arcy","sequence":"first","affiliation":[{"name":"The University of Sydney School of Chemistry, , Sydney, Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stephen J.","family":"Kolmann","sequence":"additional","affiliation":[{"name":"The University of Sydney School of Chemistry, , Sydney, Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9871-8605","authenticated-orcid":false,"given":"Meredith J. T.","family":"Jordan","sequence":"additional","affiliation":[{"name":"The University of Sydney School of Chemistry, , Sydney, Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2015,8,21]]},"reference":[{"key":"2023062602315489100_c1","doi-asserted-by":"publisher","first-page":"4013","DOI":"10.1016\/j.ijhydene.2008.05.047","volume":"33","year":"2008","journal-title":"Int. J. Hydrogen Energy"},{"key":"2023062602315489100_c2","unstructured":"U.S. Department of Energy\n          , DOE Hydrogen and Fuel Cells Program: 2014 Annual Progress Report, U.S. Department of Energy, Washington, DC, 2014."},{"key":"2023062602315489100_c3","doi-asserted-by":"publisher","first-page":"782","DOI":"10.1021\/cr200274s","volume":"112","year":"2012","journal-title":"Chem. 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