Structural, Electronic, and Magnetoresponsive Properties of Triangular Lanthanide Clusters and Their Free-Standing Nitrides
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Ημερομηνία
Συγγραφείς
Tsipis, A. C.
Stalikas, A. V.
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Εκδότης
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peer reviewed
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Όνομα περιοδικού
Journal of Computational Chemistry
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Περιγραφή
The molecular and electronic structures, stabilities, bonding features, and magnetoresponsive properties of three-membered [c-Ln(3)](+/0/-) (Ln = La, Ce, Pr, Nd, Gd, Lu) and heterocyclic six-membered [c-Ln(3)E(3)](q) (Ln = La, Ce, Pr, Nd, Gd, Lu; E = C, N; q = 0 or 1) rings have been investigated by means of electronic structure calculation methods at the DFT level. The [c-Ln(3)](+/0/-) clusters are predicted to be bound with respect to dissociation to their constituent atoms, the estimated binding energies ranging from 45.8 to 2056.4 kJ/mol. The [c-Ln(3)] rings capture easily a planar three-coordinated nitrogen atom at the center or above the center of the ring yielding the lanthanide nitride clusters [c-Ln(3)(mu(3)-N)] adopting a planar geometry, except [c-La(3)(mu(3)-N)] which exhibits pyramidal geometry. The [c-Ln(3)(mu(3)-N)] clusters are predicted to be bound, with respect to dissociation to N ((4)S) atom and [c-Ln(3)] clusters in their ground states, the binding energies ranging from 53.9 to 257.9 kcal/mol. The six-membered [c-Ln(3)E(3)](q) rings are predicted to be bound with respect to dissociation to LnE(q) monomers in their ground states with dissociation energies in the range of 173.8 to 318.0 kcal/mol. Calculation of the NICS(zz)-scan curves of the clusters predicted a "hermaphrodic" magnetic response of the [c-Ln(3)](+/0/-) and heterocyclic six-membered [c-Ln(3)E(3)](q) rings, manifested by the coexistence of successive diatropic (aromatic) and paratropic (antiaromatic) zones. The [c-La(3)](+/0/-) and [c-Lu(3)](-) are predicted to be weakly antiaromatic, the [c-Lu(3)](0/+), [c-Lu(3)C(3)](+), and [c-Lu(3)N(3)] double (sigma+pi) aromatic, and the [c-Gd(3)C(3)] and [c-Gd(3)N(3)](+) rings (sigma+delta)-aromatic systems. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 32: 620-638, 2011
Περιγραφή
Λέξεις-κλειδιά
aromaticity, dft calculations, triangular lanthanide clusters, lanthanide nitride clusters, magnetotropicity, 2nd-order perturbation-theory, density-functional theory, induced magnetic-field, nmr chemical-shifts, argon matrices, endohedral fullerenes, response properties, metal-clusters, ring currents, asymmetric catalysis
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<Go to ISI>://000287551100006
http://onlinelibrary.wiley.com/store/10.1002/jcc.21648/asset/21648_ftp.pdf?v=1&t=h0f91usw&s=8eaf7d1bb9fb7188f383f1cd8b9a4c2b843acf97
http://onlinelibrary.wiley.com/store/10.1002/jcc.21648/asset/21648_ftp.pdf?v=1&t=h0f91usw&s=8eaf7d1bb9fb7188f383f1cd8b9a4c2b843acf97
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en
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Γενική Περιγραφή / Σχόλια
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Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας