Abstract
Accurate gas phase formation enthalpies, Delta H-f, 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 Delta H-f values of these compounds in the most used databases, such as the NIST-JANAF database, are often reported with large inaccuracy, while some other Delta H-f values clearly differ from the value predicted by CCSD(T) methods. To address this point, in this work we systematically predicted the Delta H-f values of a series of these compounds having a group 4, 6, or 14 metal. The Delta H-f 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 Delta H-f values of few reference complexes. In agreement with other theoretical studies, we predict the Delta H-f 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 Delta H-f 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 Delta H-f 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).