Endohedral Metallofullerenes Containing Lanthanides: A Robust Yet Simple Computational Approach
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- 作者：Xavier Aparicio-Angl猫s ; N煤ria Alegret ; Anna Clotet ; Antonio Rodr铆guez-Fortea ; Josep M. Poblet
- 刊名：The Journal of Physical Chemistry C
- 出版年：2013
- 出版时间：June 20, 2013
- 年：2013
- 卷：117
- 期：24
- 页码：12916-12921
- 全文大小：319K
- 年卷期：v.117,no.24(June 20, 2013)
- ISSN：1932-7455
文摘
Endohedral metallofullerenes (EMFs) containing lanthanides are thoroughly analyzed using density functional theory. Our methodology, which uses planes waves as basis functions and pseudopotentials and takes into account the on-site Coulomb repulsion via the Hubbard-like U parameter, is able to reproduce the electronic structure and the main geometrical parameters for this family of compounds that presents unpaired f electrons. In addition, the relative abundances of lanthanide EMFs observed in chromatograms as well as the preference of a nitride cluster for a given fullerene are properly predicted. Cluster鈥揷age interactions are optimal when the cluster fits perfectly within the available hollow space of the carbon cage. Except for cerium nitride fullerenes, f electrons do not play a significant role in the electrochemical properties of lanthanide EMFs. If one is only interested in a qualitative prediction of the structure, reactivity, and electronic properties, then calculations that do not explicitly consider the unpaired f electrons can be acceptable.