title: Accurate Gas Phase Formation Enthalpies of Alloys and Refractories Decomposition Products.
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 ΔHfvalues of these compounds in the most used databases, such as the NIST-JANAF database, are often reported with large inaccuracy, while some other ΔHfvalues clearly differ from the value predicted by CCSD(T) methods. To address this point, in this work we systematically predicted the ΔHfvalues of a series of these compounds having a group 4, 6, or 14 metal. The ΔHfvalues 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 ΔHfvalues of few reference complexes. In agreement with other theoretical studies, we predict the ΔHfvalues for TiOCl2, TiOF2, GeF2, and SnF4to 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 ΔHfvalues for HfCl2, HfBr2, HfI2, MoOF4, MoCl6, WOF4, WOCl4, GeO2, SnO2, PbBr4, PbI4, and PbO2also 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 ΔHfvalues 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).
authors.affiliation: Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, KAUST Catalysis Center , Thuwal 23955-6900, Saudi Arabia.
authors.forename: Yury
authors.initials: Y
authors.lastname: Minenkov
authors.affiliation: Ivanovo State University of Chemistry and Technology , Research Institute for Thermodynamics and Kinetics of Chemical Processes, 153460 Ivanovo, Russian Federation.
authors.forename: Valery V
authors.initials: VV
authors.lastname: Sliznev
authors.affiliation: Physical Sciences and Engineering Division, King Abdullah University of Science and Technology, KAUST Catalysis Center , Thuwal 23955-6900, Saudi Arabia.
authors.forename: Luigi
authors.identifier: http://orcid.org/0000-0002-1398-338X
authors.initials: L
authors.lastname: Cavallo