Path integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materials

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dc.contributor.authorLindoy LP
dc.contributor.authorKolmann SJ
dc.contributor.authorD'Arcy JH
dc.contributor.authorJordan MJT
dc.contributor.authorCrittenden, Deborah
dc.date.accessioned2023-03-22T23:23:12Z
dc.date.available2023-03-22T23:23:12Z
dc.date.issued2015en
dc.date.updated2023-02-13T02:33:13Z
dc.description.abstractFinite temperature quantum and anharmonic effects are studied in H2-Li+-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, ΔUads, and enthalpy, ΔHads, 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 - coupling between the intermolecular degrees of freedom becomes less important as temperature increases whereas anharmonicity becomes more important. The most anharmonic motions in H2-Li+-benzene are the "helicopter" and "ferris wheel" 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 ΔUads and ΔHads are -13.3 ± 0.1 and -14.5 ± 0.1 kJ mol-1, respectively.en
dc.identifier.citationLindoy LP, Kolmann SJ, D'Arcy JH, Crittenden DL, Jordan MJT (2015). Path integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materials. The Journal of Chemical Physics. 143(19).en
dc.identifier.doihttp://doi.org/10.1063/1.4932940
dc.identifier.issn0021-9606
dc.identifier.issn1089-7690
dc.identifier.urihttps://hdl.handle.net/10092/105279
dc.languageEnglish
dc.language.isoenen
dc.publisherAMER INST PHYSICSen
dc.rightsAll rights reserved unless otherwise stateden
dc.rights.urihttp://hdl.handle.net/10092/17651en
dc.subjectScience & Technologyen
dc.subjectPhysical Sciencesen
dc.subjectChemistry, Physicalen
dc.subjectPhysics, Atomic, Molecular & Chemicalen
dc.subjectChemistryen
dc.subjectPhysicsen
dc.subjectMETAL-ORGANIC FRAMEWORKSen
dc.subjectPOTENTIAL-ENERGY SURFACESen
dc.subjectMOLECULAR-ORBITAL METHODSen
dc.subjectBASIS-SETSen
dc.subjectADSORPTIONen
dc.subjectINTERPOLATIONen
dc.subjectTEMPERATUREen
dc.subjectMOF-177en
dc.subjectSYSTEMSen
dc.subjectSITESen
dc.subject.anzsrc02 Physical Sciencesen
dc.subject.anzsrc03 Chemical Sciencesen
dc.subject.anzsrc09 Engineeringen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3407 - Theoretical and computational chemistry::340701 - Computational chemistryen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3402 - Inorganic chemistry::340209 - Organometallic chemistryen
dc.subject.anzsrcFields of Research::34 - Chemical sciences::3407 - Theoretical and computational chemistry::340704 - Theoretical quantum chemistryen
dc.titlePath integral Monte Carlo simulations of H2 adsorbed to lithium-doped benzene: A model for hydrogen storage materialsen
dc.typeJournal Articleen
uc.collegeFaculty of Science
uc.departmentSchool of Physical & Chemical Sciences
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