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Issue 4, 2012
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Periodic trends in electron transport through extended metal atom chains: comparison of Ru3(dpa)4(NCS)2 with its first-row analogues

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Abstract

Density functional theory is used to reconcile the structural, magnetic and electron transport properties of a triruthenium extended metal atom chain, Ru3(dpa)4(NCS)2. The distinct bending of the Ru–Ru–Ru core in this species is traced to strong second-order mixing between levels of σ and π symmetry that are near degenerate in the linear geometry. The dominant electron transport channel is formed by the LUMO, an orbital of π* symmetry that lies just above the Fermi level of the gold electrode. The bending has a substantial impact on electron transport in that it induces a spin crossover from a quintet to a singlet which in turn brings the LUMO much closer to the Fermi level. The presence of significant net π bonding in the metal chains also broadens the π/πnb/π* manifold, such that the channel is not strongly perturbed by the electric field, even at a bias of 1.0 V. The presence of a robust π symmetry conduction channel marks the triruthenium systems out as quite distinct from its first-row counterparts, Cr3(dpa)4(NCS)2 and Co3(dpa)4(NCS)2, where current flows primarily through the σ framework.

Graphical abstract: Periodic trends in electron transport through extended metal atom chains: comparison of Ru3(dpa)4(NCS)2 with its first-row analogues

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Publication details

The article was received on 06 Dec 2011, accepted on 31 Jan 2012 and first published on 31 Jan 2012


Article type: Edge Article
DOI: 10.1039/C2SC01024K
Citation: Chem. Sci., 2012,3, 1319-1329
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    Periodic trends in electron transport through extended metal atom chains: comparison of Ru3(dpa)4(NCS)2 with its first-row analogues

    P. J. Mohan, V. P. Georgiev and J. E. McGrady, Chem. Sci., 2012, 3, 1319
    DOI: 10.1039/C2SC01024K

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