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dc.contributor.authorMinenkova, Irina
dc.contributor.authorOsina, Evgeniya L.
dc.contributor.authorCavallo, Luigi
dc.contributor.authorMinenkov, Yury
dc.date.accessioned2020-11-22T12:56:44Z
dc.date.available2020-11-22T12:56:44Z
dc.date.issued2020-11-19
dc.date.submitted2020-08-01
dc.identifier.citationMinenkova, I., Osina, E. L., Cavallo, L., & Minenkov, Y. (2020). Gas-Phase Thermochemistry of MX3 and M2X6 (M = Sc, Y; X = F, Cl, Br, I) from a Composite Reaction-Based Approach: Homolytic versus Heterolytic Cleavage. Inorganic Chemistry. doi:10.1021/acs.inorgchem.0c02292
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.pmid33210914
dc.identifier.doi10.1021/acs.inorgchem.0c02292
dc.identifier.urihttp://hdl.handle.net/10754/666069
dc.description.abstractA domain-based local-pair natural-orbital coupled-cluster approach with single, double, and improved linear-scaling perturbative triple correction via an iterative algorithm, DLPNO-CCSD(T1), was applied within the framework of the Feller-Peterson-Dixon approach to derive gas-phase heats of formation of scandium and yttrium trihalides and their dimers via a set of homolytic and heterolytic dissociation reactions. All predicted heats of formation moderately depend on the reaction type with the most and least negative values obtained for homolytic and heterolytic dissociation, respectively. The basis set size dependence, as well as the influence of static correlation effects not covered by the standard (DLPNO-)CCSD(T) approach, suggests that exploitation of the heterolytic dissociation reactions with the formation of M3+ and X- ions leads to the most robust heats of formation. The gas-phase formation enthalpies ΔHf°(0 K)/ΔHf°(298.15 K) and absolute entropies S°(298.15 K) were obtained for the first time for the Sc2F6, Sc2Br6, and Sc2I6 species. For ScBr3, ScI3, Sc2Cl6, and Y2Cl6, we suggest a reexamination of the experimental heats of formation available in the literature. For other compounds, the predicted values were found to be in good agreement with the experimental estimates. Extracted MX3 (M = Sc, Y; X = F, Cl, Br, and I) 0 K atomization enthalpies indicate weaker bonding when moving from fluorine to iodine and from yttrium to scandium. Likewise, the stability of yttrium trihalide dimers degrades when going from fluorine to iodine. Respective scandium trihalide dimers are less stable, with 0 K dimer dissociation energy decreasing in the row fluorine - chlorine - bromine ≈ iodine. Correlation of the (n - 1)s2p6 electrons on bromine and iodine, inclusion of zero-point energy, relativistic effects, and the effective-core-potential correction as well as amelioration of the DLPNO localization inaccuracy are shown to be of similar magnitude, which is critical if accurate heats of formation are a goal.
dc.description.sponsorshipWe gratefully acknowledge Dr. Valery V. Sliznev, Ivanovo State University of Chemistry and Technology, Ivanovo, Russia, for helpful discussions.
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02292
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c02292.
dc.titleGas-Phase Thermochemistry of MX3 and M2X6 (M = Sc, Y; X = F, Cl, Br, I) from a Composite Reaction-Based Approach: Homolytic versus Heterolytic Cleavage
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalInorganic Chemistry
dc.rights.embargodate2021-11-19
dc.eprint.versionPost-print
dc.contributor.institutionFrumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow 119071, Russia
dc.contributor.institutionJoint Institute for High Temperatures, Russian Academy of Sciences, 13-2 Izhorskaya Street, Moscow 125412, Russia
dc.contributor.institutionN.N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Kosygina Street 4, Moscow 119991, Russia
kaust.personCavallo, Luigi
refterms.dateFOA2020-11-23T06:24:16Z


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