Precise Identification of the Infrared Bands of the Polycarbonyl Complexes on Ni鈥揗OR Zeolite by 12C16O鈥?sup>13C18O Coadsorption and Computational Modeling
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- 作者：Hristiyan A. Aleksandrov ; Videlina R. Zdravkova ; Mihail Y. Mihaylov ; Petko St. Petkov ; Georgi N. Vayssilov ; Konstantin I. Hadjiivanov
- 刊名：The Journal of Physical Chemistry C
- 出版年：2012
- 出版时间：November 1, 2012
- 年：2012
- 卷：116
- 期：43
- 页码：22823-22831
- 全文大小：478K
- 年卷期：v.116,no.43(November 1, 2012)
- ISSN：1932-7455
文摘
We report a combined computational and experimental IR study of polycarbonyl species on Ni鈥揗OR zeolite formed after adsorption of 12C16O/13C18O isotopic mixtures, which allowed us to suggest a justified assignment of the vibrational bands in the complex IR spectra. For identification of all individual IR bands of the polycarbonyl complexes containing either the same or mixed isotopic probe molecules, we modeled the corresponding species with density functional method. In order to provide reliable computed values for comparison with experimentally measured vibrational frequencies of CO in the complexes, we combined periodic density functional calculations (with gradient corrected exchange-correlation functional) with isolated cluster calculations using hybrid functional. In this way, we confirm that the Ni+ cations in this zeolite material are able to form di- and tricarbonyl complexes and thus feature high coordinative unsaturation as suggested earlier.