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Spin and Structural Features in Oxygen Dissociation on Tetrahedral Ag20 and Ag19Au Clustersстатья
Статья опубликована в высокорейтинговом журнале
Информация о цитировании статьи получена из
Web of Science,
Scopus
Статья опубликована в журнале из списка Web of Science и/или Scopus
Дата последнего поиска статьи во внешних источниках: 2 сентября 2016 г.
- Авторы: Pichugina D.A., Polynskaya Y.G., Kuz’menko N.E.
- Журнал: Physical Chemistry Chemical Physics
- Том: 18
- Год издания: 2016
- Издательство: Royal Society of Chemistry
- Местоположение издательства: United Kingdom
- Первая страница: 18033
- Последняя страница: 18044
- DOI: 10.1039/C6CP01630H
- Аннотация: The spin-crossing mechanism of oxygen dissociation on Ag20 and monodoped Ag19Au clusters was investigated by spin–polarized scalar-relativistic DFT calculations using the PBE, TPSSh, M06L, mPBE, BLYP, OLYP, and B3LYP. In particular, the singlet and triplet O–O bond rupture pathways at vertex-edge and facet-edge sites on the tetrahedral clusters were studied. The calculations reveal that for the Ag20O2 and Ag19AuO2 complexes, the spin inversion from the triplet to singlet state occurs during the last step, which involves O–O bond rupture through a singlet transition state (TS). When spin crossing during oxygen dissociation on the clusters is considered, the activation energies decrease by 10-29 kJ/mol; however, they are still high due to the magic nature of the clusters and high vertical spin excitation energies. For these silver clusters, size effects based on the relationship between the TS structure and oxidation activation energy were predicted.
- Добавил в систему: Полынская (Сныга) Юлия Геннадьевна