Structural, Electronic, and Magnetoresponsive Properties of Triangular Lanthanide Clusters and Their Free-Standing Nitrides

 
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2011 (EN)
Structural, Electronic, and Magnetoresponsive Properties of Triangular Lanthanide Clusters and Their Free-Standing Nitrides (EN)

Tsipis, A. C. (EN)

Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας (EL)
Tsipis, A. C. (EN)

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 (EN)

aromaticity (EN)

Πανεπιστήμιο Ιωαννίνων (EL)
University of Ioannina (EN)

Journal of Computational Chemistry (EN)

English

2011

<Go to ISI>://000287551100006



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