Structure, Stability, and Cluster-Cage Interactions in Nitride Clusterfullerenes MN@C (M = Sc, Y; 2n = 68-98): a Density Functional Theory Study.
Extensive semiempirical calculations of the hexaanions of PR (isolated pentagon rule) and non-IPR isomers of C-C and IPR isomers of C-C followed by DFT calculations of the lowest energy structures were performed to find the carbon cages that can provide the most stable isomers of MN@C clustertullere...
| Published in: | Journal of the American Chemical Society Vol. 129; no. 38; pp. 11835 - 11850 |
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| Main Authors: | , |
| Format: | Article |
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American Chemical Society
9/26/2007
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| Online Access: | View this record in EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=26995662&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 26995662 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 9/26/2007 vid: 129 iid: 38 pid: 997 pub: American Chemical Society artinfo: ui: 26995662 10.1021/ja073809l ppf: 11835 ppct: 15 formats: tig: atl: Structure, Stability, and Cluster-Cage Interactions in Nitride Clusterfullerenes MN@C (M = Sc, Y; 2n = 68-98): a Density Functional Theory Study. aug: au: Popov, Alexey A. Dunsch, Lothar affil: Moscow State University Leibniz-Institute for Solid State and Materials Research Dresden su: Chemical structure Physical & theoretical chemistry Nitrides Density functionals Anions Rare earth ions sug: subj: Chemical structure Physical & theoretical chemistry Nitrides Density functionals Anions Rare earth ions ab: Extensive semiempirical calculations of the hexaanions of PR (isolated pentagon rule) and non-IPR isomers of C-C and IPR isomers of C-C followed by DFT calculations of the lowest energy structures were performed to find the carbon cages that can provide the most stable isomers of MN@C clustertullerenes (M = Sc, Y) withY as a model for rare earth ions. DFT calculations of isomers of MN@C (M = Sc, Y; 2n = 68-98) based on the most stable C cages were also performed. The lowest energy isomers found by this methodology for ScN@C, ScN@C, ScN@C, YN@C, YN@C, YN@C, YN@C, and YN@C are those that have been shown to exist by single-crystal X-ray studies as ScN@C (2n = 68, 78, 80), DyN@C, and TbN@C (2n = 80, 84, 86, 88) clusterfullerenes. Reassignment of the carbon cage of Sc@C to the non-IPR C: 17490 isomer is also proposed. The stability of nitride clustertullerenes was found to correlate well with the stability of the empty 6-fold charged cages. However, the dimensions of the cage in terms of its ability to encapsulate MN clusters were also found to be an important factor, especially for the medium size cages and the large YN cluster. In some cases the most stable structures are based on the different cage isomers for ScN and YN clusters. Up to the cage size of C, non-IPR isomers of C and MN@C were found to compete with or to be even more stable than IPR isomers. However, the number of adjacent pentagon pairs in the most stable non- IPR isomers decreases as cage size increases: the most stable MN@C isomers have three such pairs for 2n = 68–72, two pairs for n = 74–80, and only one pair for n = 82, 84. For C and C the lowest energy IPR isomers are much more stable than any non-IPR isomer. The trends in the stability of the fullerene isomers and the cluster-cage binding energies are discussed, and general rules for stability of clustertullerenes are established. Finally, the high yield of MN@C (I) clustertullerenes for any metal is explained by the exceptional stability of the C (I: 31924) cage, rationalized by the optimum distribution of the pentagons leading to the minimization of the steric strain, and structural similarities of C (I: 31924) with the lowest energy non-IPR isomers of C, C, C, and C pointed out. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2007 holdings: @attributes: islocal: N |
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