Document Type
Article
Department or Administrative Unit
Chemistry
Publication Date
11-5-2015
Abstract
Titanium dioxide (TiO2) nanoparticles are widely used in contaminant remediation, photocatalysis, and solar cell manufacturing. The low-cost production of TiO2 nanoparticles via the combustion of titanium tetrachloride (TiCl4) in oxygen is thus an important industrial process. To accurately model the flame synthesis of TiO2 nanoparticles, reliable thermodynamic data of Ti-O-Cl species are indispensable but often unavailable. We therefore carried out benchmark calculations, using the left-eigenstate completely renormalized singles, doubles, and perturbative triples (CR-CC(2,3), aka CR-CCL) method with the cc-pVTZ basis set, to obtain the equilibrium structures and vibrational frequencies of selected Ti-O-Cl species; we then performed single-point CCSD(T)/aug-cc-pVLZ (L = 3-5) calculations to extrapolate the CCSD(T)/CBS energies. After analyzing the experimental and calculated enthalpy of selected Ti-O-Cl species, the standard enthalpy of formation of the TiOCl2 molecule is determined to be -600.5 kJ/mol at 298 K. The standard enthalpy of all other Ti-O-Cl species are determined accordingly. Finally, we assessed the accuracy of 42 popular density functionals for the Ti-O-Cl species. Among these assessed functionals, the B98 functional, tightly followed by B97-1 and B3LYP, exhibits the best overall performance in the prediction of the thermochemistry of the Ti-O-Cl species.
Recommended Citation
Ge, Yingbin; DePrekel, Douglas; Lam, Kui-Ting; Ngo, Kevin; and Vo, Phu, "Assessing density functionals for the prediction of thermochemistry of Ti-O-Cl species" (2015). All Faculty Scholarship for the College of the Sciences. 149.
https://digitalcommons.cwu.edu/cotsfac/149
Journal
Journal of Theoretical and Computational Chemistry
Rights
© World Scientific Publishing Co Ltd
Comments
The download link on this page is to an accepted manuscript version of this article and may not be the final version of this article.
Electronic version of an article published as Journal of Theoretical and Computational Chemistry Vol. 14, No. 08, (2015) DOI: 10.1142/S0219633615500558 © World Scientific Publishing Company https://www.worldscientific.com/worldscinet/jtcc
This article was originally published in Journal of Theoretical and Computational Chemistry. The full-text article from the publisher can be found here.