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Hindered Cluster Rotation and (45)Sc Hyperfine Splitting Constant in Distonoid Anion Radical Sc(3)N@C(80)(-), and Spatial Spin-Charge Separation as a General Principle for Anions of Endohedral Fullerenes with Metal-Localized Lowest Unoccupied Molecular Orbitals.

Popov, A and Dunsch, L (2008) Hindered Cluster Rotation and (45)Sc Hyperfine Splitting Constant in Distonoid Anion Radical Sc(3)N@C(80)(-), and Spatial Spin-Charge Separation as a General Principle for Anions of Endohedral Fullerenes with Metal-Localized Lowest Unoccupied Molecular Orbitals. Journal of the American Chemical Society . ISSN 1520-5126

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ja804226a

Abstract

DFT calculations of Sc(3)N@C(80) in the neutral and anionic states are performed which revealed that in the neutral state of the nitride clusterfullerene the lowest energy structure has C(3) symmetry, while in the anionic and dianionic states the C(3v) conformer has the lowest energy. Barriers to the cluster rotation inside the cage are also found to increase in the charge states. The (45)Sc hyperfine slitting constant, a(Sc), in Sc(3)N@C(80) anion radical is calculated by different theoretical approaches and in different conformations of Sc(3)N cluster. It is found that a(Sc) is strongly dependent on the cluster orientation with respect to the cage, covering a range form -10 to +25 Gauss at the B3LYP/6-311G*//PBE/TZ2P level of theory. A thorough analysis of the computed values as well as comparison of unrestricted and orbital-restricted calculations revealed that the polarization contribution to a(Sc) is about -10 Gauss and does not depend on the cluster orientation. Dependence of the predicted a(Sc) values on the density functional form (LSDA, BP, PBE, BLYP, OLYP, TPSS, B3LYP, and TPSSh), the basis set, as well as on the scalar-relativistic and spin-orbit corrections were investigated. The analysis of the charge distribution in the Sc(3)N@C(80)(-) anion radical revealed an interesting peculiarity of its electronic structure: while the spin density mostly resides on the cluster, only a slight decrease of its charge is found using both Bader and Mulliken definitions of atomic charges. A set of other endohedral metallofullerenes, including nitride clusterfullerenes Sc(3)N@C(2n) (2n = 68, 70, 78) and Y(3)N@C(2n) (2n = 78-88), carbide clusterfullerenes Sc(2)C(2)@C(68), Sc(2)C(2)@C(82), Sc(3)C(2)@C(80), Ti(2)C(2)@C(78), Y(2)C(2)@C(82), and dimetallofullerenes Sc(2)@C(76), Y(2)@C(82), La(2)@C(2n) (2n = 72, 78, 80), was also studied in the neutral and anionic state, and a spatial charge-spin separation is found to be a general rule for all endohedral fullerenes with high contribution of metal atoms to the LUMO.

Item Type:Article
Subjects:Physical Science > Nanophysics
Physical Science > Nanoelectronics
Physical Science > Quantum phenomena
Divisions:Faculty of Engineering, Science and Mathematics > School of Mathematics
ID Code:416
Deposited By:Lesley Tobin
Deposited On:03 Dec 2008 17:28
Last Modified:09 Feb 2009 17:04

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