{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,17]],"date-time":"2026-08-17T22:21:51Z","timestamp":1787005311689,"version":"build-2736575974"},"reference-count":50,"publisher":"AIP Publishing","issue":"19","funder":[{"DOI":"10.13039\/501100000923","name":"Australian Research Council","doi-asserted-by":"crossref","award":["DP0665065"],"award-info":[{"award-number":["DP0665065"]}],"id":[{"id":"10.13039\/501100000923","id-type":"DOI","asserted-by":"crossref"}]},{"DOI":"10.13039\/501100001774","name":"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":[[2015,11,21]]},"abstract":"<jats:p>Finite temperature quantum and anharmonic effects are studied in H2\u2013Li+-benzene, a model hydrogen storage material, using path integral Monte Carlo (PIMC) simulations on an interpolated potential energy surface refined over the eight intermolecular degrees of freedom based upon M05-2X\/6-311+G(2df,p) density functional theory calculations. Rigid-body PIMC simulations are performed at temperatures ranging from 77 K to 150 K, producing both quantum and classical probability density histograms describing the adsorbed H2. Quantum effects broaden the histograms with respect to their classical analogues and increase the expectation values of the radial and angular polar coordinates describing the location of the center-of-mass of the H2 molecule. The rigid-body PIMC simulations also provide estimates of the change in internal energy, \u0394Uads, and enthalpy, \u0394Hads, for H2 adsorption onto Li+-benzene, as a function of temperature. These estimates indicate that quantum effects are important even at room temperature and classical results should be interpreted with caution. Our results also show that anharmonicity is more important in the calculation of U and H than coupling\u2014coupling between the intermolecular degrees of freedom becomes less important as temperature increases whereas anharmonicity becomes more important. The most anharmonic motions in H2\u2013Li+-benzene are the \u201chelicopter\u201d and \u201cferris wheel\u201d H2 rotations. Treating these motions as one-dimensional free and hindered rotors, respectively, provides simple corrections to standard harmonic oscillator, rigid rotor thermochemical expressions for internal energy and enthalpy that encapsulate the majority of the anharmonicity. At 150 K, our best rigid-body PIMC estimates for \u0394Uads and \u0394Hads are \u221213.3 \u00b1 0.1 and \u221214.5 \u00b1 0.1 kJ mol\u22121, respectively.<\/jats:p>","DOI":"10.1063\/1.4932940","type":"journal-article","created":{"date-parts":[[2015,11,17]],"date-time":"2015-11-17T13:00:58Z","timestamp":1447765258000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":12,"title":["Path integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materials"],"prefix":"10.1063","volume":"143","author":[{"given":"Lachlan P.","family":"Lindoy","sequence":"first","affiliation":[{"name":"The University of Sydney 1 School of Chemistry, , Sydney, Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Stephen J.","family":"Kolmann","sequence":"additional","affiliation":[{"name":"The University of Sydney 1 School of Chemistry, , Sydney, Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3309-064X","authenticated-orcid":false,"given":"Jordan H.","family":"D\u2019Arcy","sequence":"additional","affiliation":[{"name":"The University of Sydney 1 School of Chemistry, , Sydney, Australia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Deborah L.","family":"Crittenden","sequence":"additional","affiliation":[{"name":"University of Canterbury 2 Department of Chemistry, , Christchurch, New Zealand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9871-8605","authenticated-orcid":false,"given":"Meredith J. 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