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Thermochemistry of SinOx(OH)y Vapor Species from Quantum Chemical Calculations.
Bauschlicher, Charles W; Jacobson, Nathan S; Fegley, Bruce.
Afiliación
  • Bauschlicher CW; NASA Ames Research Center, Moffett Field, California 94035, United States.
  • Jacobson NS; NASA Glenn Research Center/HX5, LLC, Cleveland, Ohio 44135, United States.
  • Fegley B; Washington University at St. Louis, St. Louis, Missouri 63130, United States.
J Phys Chem A ; 127(42): 8892-8899, 2023 Oct 26.
Article en En | MEDLINE | ID: mdl-37823800
The thermochemistry of the Si-O-H system has been extensively studied both experimentally and theoretically due to its importance in chemical processes, degradation of silica-protected materials in combustion, and geological processes. In this paper, we review past studies and use quantum mechanical methods to generate a new data set. Molecular geometries were generated with DFT using the B3LYP functional. Energetics were calculated with RCCSD(T) methods extrapolated to the complete basis set (CBS/45) limit. Particular attention was given to the treatment of the vibrational modes. A rigid rotor model was used, corrections for anharmonicity were applied, and the Pitzer-Gwinn treatment of the hindered rotation of the M-OH groups was applied. The generated enthalpies of formation at 298 K are compared to those of experiments and other calculations. Generally, the agreement is good. A set of thermodynamic data (enthalpy of formation at 298 K, entropy at 298 K, and heat capacity polynomial to 3000 K) is presented for SiOH, SiO(OH), Si(OH)2, SiO(OH)2, Si(OH)3, Si(OH)4, Si2O(OH)6, and Si3O2(OH)8. These can be added to any of the common computational thermodynamics packages. The application of these data to high-temperature corrosion and geological problems is discussed.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem A Asunto de la revista: QUIMICA Año: 2023 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem A Asunto de la revista: QUIMICA Año: 2023 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos