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On the accuracy of density-functional methods for determining structures of dicationic binuclear ruthenocene derivatives bridged by an unsaturated molecule
en
ruthenocene derivatives
density-functional theory
electronic structure
molecular wire
高柳 敏幸
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM
806
1-3
85-92
2007
2007-3
ELSEVIER SCIENCE BV
01661280
info:doi/10.1016/j.theochem.2006.11.011
http://www.sciencedirect.com/science/journal/01661280|http://www.sciencedirect.com/science/journal/01661280
Various exchange and correlation functionals have been examined in density-functional calculations for obtaining reliable optimized structures for dicationic binuclear ruthenocenes bridged by an unsaturated compound, which has a characteristic fulvene-type structure. First, we have performed extensive calculations for ruthenocene (RuCp2) in D-5h symmetry. It has been found that the Ru-Cp optimized distance is linearly correlated with the energy difference between highest occupied a(1)' and e(2)' orbitals. We have then found that the optimized structure of dicationic binuclear ruthenocenes is strongly dependent of the a(1)'-e(2)' orbital sequence observed in RuCp2. In particular, when exchange-correlation functionals giving the a(1)' < e(2)' orbital sequence are employed, the contribution of the fulvene-type structure is found to be significantly underestimated in the optimized structure of dicationic binuclear ruthenocenes. We finally demonstrate that the SVWN exchange-correlation functionals give reasonable optimized structures comparable to experimental structures determined by X-ray crystallography analysis. (c) 2006 Elsevier B.V. All rights reserved.
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2008-01-24