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dc.contributor.authorAriyarathna, Isuru R.
dc.contributor.authorCho, Yeongsu
dc.contributor.authorDuan, Chenru
dc.contributor.authorKulik, Heather J.
dc.date.accessioned2024-04-12T16:37:43Z
dc.date.available2024-04-12T16:37:43Z
dc.date.issued2023
dc.identifier.issn1463-9076
dc.identifier.issn1463-9084
dc.identifier.urihttps://hdl.handle.net/1721.1/154137
dc.description.abstractAb initio multi-reference configuration interaction (MRCI) and coupled cluster singles doubles and perturbative triples [CCSD(T)] levels of theory were used to study ground and excited electronic states of HfCO. We report potential energy curves, dissociation energies (De), excitation energies, harmonic vibrational frequencies, and chemical bonding patterns of HfCO. The 3Σ− ground state of HfCO has an 1σ22σ21π2 electron configuration and a ∼30 kcal mol−1 dissociation energy with respect to its lowest-energy fragments Hf(3F) + CO(X1Σ+). We further evaluated the De of its isovalent HfCX (X = S, Se, Te, Po) series and observed that they increase linearly from the lighter HfCO to the heavier HfCPo with the dipole moment of the CX ligand. The same linear relationship was observed for TiCX and ZrCX. We utilized the CCSD(T) benchmark values of De, excitation energy, and ionization energy (IE) values to evaluate density functional theory (DFT) errors with 23 exchange–correlation functionals spanning GGA, meta-GGA, global GGA hybrid, meta-GGA hybrid, range-separated hybrid, and double-hybrid functional families. The global GGA hybrid B3LYP and range-separated hybrid ωB97X performed well at representing the ground state properties of HfCO (i.e., De and IE). Finally, we extended our DFT analysis to the interaction of a CO molecule with a Hf surface and observed that the surface chemisorption energy and the gas-phase molecular dissociation energy are very similar for some DFAs but not others, suggesting moderate transferability of the benchmarks on these molecules to the solid state.en_US
dc.description.sponsorshipU.S. Department of Energyen_US
dc.publisherRoyal Society of Chemistry (RSC)en_US
dc.relation.isversionof10.1039/d3cp03550fen_US
dc.rightsCreative Commons Attributionen_US
dc.rights.urihttps://creativecommons.org/licenses/by-nc/3.0/en_US
dc.sourceRoyal Society of Chemistryen_US
dc.subjectPhysical and Theoretical Chemistryen_US
dc.subjectGeneral Physics and Astronomyen_US
dc.titleGas-phase and solid-state electronic structure analysis and DFT benchmarking of HfCOen_US
dc.typeArticleen_US
dc.identifier.citationAriyarathna, Isuru R., Cho, Yeongsu, Duan, Chenru and Kulik, Heather J. 2023. "Gas-phase and solid-state electronic structure analysis and DFT benchmarking of HfCO." Physical Chemistry Chemical Physics, 25 (39).
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemical Engineering
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistry
dc.relation.journalPhysical Chemistry Chemical Physicsen_US
dc.identifier.mitlicensePUBLISHER_CC
dc.eprint.versionFinal published versionen_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dspace.date.submission2024-04-12T13:59:24Z
mit.journal.volume25en_US
mit.journal.issue39en_US
mit.licensePUBLISHER_CC
mit.metadata.statusAuthority Work and Publication Information Neededen_US


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