Modeling of MAl12 Keggin Heteroatom Reactivity by Anion Adsorption
| Autor: | Joseph W. Bennett, Jennifer L. Bjorklund, Tori Z. Forbes, Sara E. Mason |
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| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
Chemistry Heteroatom Intermolecular force General Chemistry 010402 general chemistry Condensed Matter Physics 01 natural sciences 0104 chemical sciences Nanoclusters Bond length Adsorption Molecular vibration Physical chemistry General Materials Science Density functional theory Reactivity (chemistry) |
| Zdroj: | Crystal Growth & Design. 19:2820-2829 |
| ISSN: | 1528-7505 1528-7483 |
| DOI: | 10.1021/acs.cgd.9b00044 |
| Popis: | Heteroatom-substituted Keggins, of general formula MAl12 (M = Al, Ga, Ge), are a class of nanoclusters whose properties are sensitive to changes in composition and intermolecular interactions. Previous studies have shown that they display significant differences in oxygen-isotope exchange rates, depending on the identity of heteroatom M. By exploring the intermolecular interactions of these nanoclusters with a series of anions using density functional theory (DFT) calculations, we find bond length changes and adsorption energy values that track with experimentally measured oxygen exchange reactivity trends: Ga < Al < Ge. We compare elongations in μ4O–Alo bond lengths to known heteroatom reactivity trends and anion pKa properties, suggesting a window for producing isolable products. To yield insights into the atomistic interactions that dictate the crystallization process, we investigate trends in adsorption energy, DFT-optimized geometries, and vibrational modes and calculate the distribution of charge in... |
| Databáze: | OpenAIRE |
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