Accurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Products

Handle URI:
http://hdl.handle.net/10754/622806
Title:
Accurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Products
Authors:
Minenkov, Yury; Sliznev, Valery V.; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
Accurate gas phase formation enthalpies, ΔHf, of metal oxides and halides are critical for the prediction of the stability of high temperature materials used in the aerospace and nuclear industries. Unfortunately, the experimental ΔHf values of these compounds in the most used databases, such as the NIST-JANAF database, are often reported with large inaccuracy, while some other ΔHf values clearly differ from the value predicted by CCSD(T) methods. To address this point, in this work we systematically predicted the ΔHf values of a series of these compounds having a group 4, 6, or 14 metal. The ΔHf values in question were derived within a composite Feller-Dixon-Peterson (FDP) scheme based protocol that combines the DLPNO-CCSD(T) enthalpy of ad hoc designed reactions and the experimental ΔHf values of few reference complexes. In agreement with other theoretical studies, we predict the ΔHf values for TiOCl2, TiOF2, GeF2, and SnF4 to be significantly different from the values tabulated in NIST-JANAF and other sources, which suggests that the tabulated experimental values are inaccurate. Similarly, the predicted ΔHf values for HfCl2, HfBr2, HfI2, MoOF4, MoCl6, WOF4, WOCl4, GeO2, SnO2, PbBr4, PbI4, and PbO2 also clearly differ from the tabulated experimental values, again suggesting large inaccuracy in the experimental values. In the case when largely different experimental values are available, we point to the value that is in better agreement with our results. We expect the ΔHf values reported in this work to be quite accurate, and thus, they might be used in thermodynamic calculations, because the effects from core correlation, relativistic effects, and basis set incompleteness were included in the DLPNO-CCSD(T) calculations. T1 and T2 values were thoroughly monitored as indicators of the quality of the reference Hartree-Fock orbitals (T1) and potential multireference character of the systems (T2).
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Minenkov Y, Sliznev VV, Cavallo L (2017) Accurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Products. Inorganic Chemistry. Available: http://dx.doi.org/10.1021/acs.inorgchem.6b02441.
Publisher:
American Chemical Society (ACS)
Journal:
Inorganic Chemistry
Issue Date:
17-Jan-2017
DOI:
10.1021/acs.inorgchem.6b02441
Type:
Article
ISSN:
0020-1669; 1520-510X
Sponsors:
We gratefully acknowledge Edriss Chermak, SABIC, for helpful discussions. We also gratefully acknowledge Frank Neese and Frank Wennmohs, Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr, Germany, for providing us the prerelease version of ORCA. The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia.
Additional Links:
http://pubs.acs.org/doi/full/10.1021/acs.inorgchem.6b02441
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorMinenkov, Yuryen
dc.contributor.authorSliznev, Valery V.en
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2017-01-29T13:51:40Z-
dc.date.available2017-01-29T13:51:40Z-
dc.date.issued2017-01-17en
dc.identifier.citationMinenkov Y, Sliznev VV, Cavallo L (2017) Accurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Products. Inorganic Chemistry. Available: http://dx.doi.org/10.1021/acs.inorgchem.6b02441.en
dc.identifier.issn0020-1669en
dc.identifier.issn1520-510Xen
dc.identifier.doi10.1021/acs.inorgchem.6b02441en
dc.identifier.urihttp://hdl.handle.net/10754/622806-
dc.description.abstractAccurate gas phase formation enthalpies, ΔHf, of metal oxides and halides are critical for the prediction of the stability of high temperature materials used in the aerospace and nuclear industries. Unfortunately, the experimental ΔHf values of these compounds in the most used databases, such as the NIST-JANAF database, are often reported with large inaccuracy, while some other ΔHf values clearly differ from the value predicted by CCSD(T) methods. To address this point, in this work we systematically predicted the ΔHf values of a series of these compounds having a group 4, 6, or 14 metal. The ΔHf values in question were derived within a composite Feller-Dixon-Peterson (FDP) scheme based protocol that combines the DLPNO-CCSD(T) enthalpy of ad hoc designed reactions and the experimental ΔHf values of few reference complexes. In agreement with other theoretical studies, we predict the ΔHf values for TiOCl2, TiOF2, GeF2, and SnF4 to be significantly different from the values tabulated in NIST-JANAF and other sources, which suggests that the tabulated experimental values are inaccurate. Similarly, the predicted ΔHf values for HfCl2, HfBr2, HfI2, MoOF4, MoCl6, WOF4, WOCl4, GeO2, SnO2, PbBr4, PbI4, and PbO2 also clearly differ from the tabulated experimental values, again suggesting large inaccuracy in the experimental values. In the case when largely different experimental values are available, we point to the value that is in better agreement with our results. We expect the ΔHf values reported in this work to be quite accurate, and thus, they might be used in thermodynamic calculations, because the effects from core correlation, relativistic effects, and basis set incompleteness were included in the DLPNO-CCSD(T) calculations. T1 and T2 values were thoroughly monitored as indicators of the quality of the reference Hartree-Fock orbitals (T1) and potential multireference character of the systems (T2).en
dc.description.sponsorshipWe gratefully acknowledge Edriss Chermak, SABIC, for helpful discussions. We also gratefully acknowledge Frank Neese and Frank Wennmohs, Max Planck Institute for Chemical Energy Conversion, Mülheim an der Ruhr, Germany, for providing us the prerelease version of ORCA. The research reported in this publication was supported by funding from King Abdullah University of Science and Technology (KAUST). For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science and Technology (KAUST) in Thuwal, Saudi Arabia.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/full/10.1021/acs.inorgchem.6b02441en
dc.titleAccurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Productsen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalInorganic Chemistryen
dc.contributor.institutionIvanovo State University of Chemistry and Technology , Research Institute for Thermodynamics and Kinetics of Chemical Processes, 153460 Ivanovo, Russian Federation.en
kaust.authorMinenkov, Yuryen
kaust.authorCavallo, Luigien
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