Computational Study of the Hydrolysis Reactions of Small MO2 (M = Zr and Hf) Nanoclusters with Water
| Autor: | James L. Gole, Natalie W. Gist, David A. Dixon, Shenggang Li, Zongtang Fang, Matthew D. Outlaw, Kyle K.G. Smith |
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| Rok vydání: | 2012 |
| Předmět: |
Chemistry
Photochemistry Surfaces Coatings and Films Electronic Optical and Magnetic Materials Nanoclusters Metal Partial charge General Energy Adsorption Physisorption visual_art visual_art.visual_art_medium Physical chemistry Density functional theory Singlet state Physical and Theoretical Chemistry Triplet state |
| Zdroj: | The Journal of Physical Chemistry C. 116:8475-8492 |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/jp210867w |
| Popis: | Density functional theory (DFT) has been used to study the hydrolysis reaction of (MO2)n (M = Zr, Hf, n = 1–4) nanoclusters in the ground singlet and first triplet states. The reactions for singlet n = 1 were benchmarked at the CCSD(T) level of theory. The reactions of H2O with the metal site having an M═O bond and/or M–O bonds as well as H transfer to both terminal ═O atoms and bridge −O atoms have been studied. The partial charge on M increases as the M═O bonds are replaced with M–OH bonds. The first H2O adsorption (physisorption) energies for these MO2 nanoclusters are calculated to be −20 to −30 kcal/mol for the singlet state and −15 to −48 kcal/mol for the triplet state. These physisorption energies depend on the cluster size and the adsorption site, consistent with existing experimental and computational studies. The first hydrolysis (dissociative chemisorption) reaction energies of the MO2 nanoclusters are calculated to have a much broader range, −30 to −80 kcal/mol for the singlet states and −30 t... |
| Databáze: | OpenAIRE |
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