Issue 17, 2019

Helical orbitals and circular currents in linear carbon wires

Abstract

Disubstituted odd-carbon cumulenes are linear carbon wires with near-degenerate helical π-orbitals. Such cumulenes are chiral molecules but their electronic structure consists of helical orbitals of both chiralities. For these helical molecular orbitals to give rise to experimentally observable effects, the near-degenerate orbitals of opposite helicities must be split. Here we show how pyramidalized single-faced π-donors, such as the amine substituent, provide a strategy for splitting the helical molecular orbitals. The chirality induced by the amine substituents allow for systematic control of the helicity of the frontier orbitals. We examine how the helical orbitals in odd-carbon cumulenes control the coherent electron transport properties, and we explicitly predict two modes in the experimental single-molecule conductance for these molecules. We also show that the current density through these linear wires exhibits strong circular currents. The direction of the circular currents is systematically controlled by the helicity of the frontier molecular orbitals, and is therefore altered by changing between the conformations of the molecule. Furthermore, the circular currents are subject to a full ring-reversal around antiresonances in the Landauer transmission, emphasizing the relation to destructive quantum interference. With circular currents present around truly linear carbon wires, cumulenes are promising candidates for novel applications in molecular electronics.

Graphical abstract: Helical orbitals and circular currents in linear carbon wires

Associated articles

Supplementary files

Article information

Article type
Edge Article
Submitted
06 Des 2018
Accepted
14 Mac 2019
First published
19 Mac 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 4598-4608

Helical orbitals and circular currents in linear carbon wires

M. H. Garner, A. Jensen, L. O. H. Hyllested and G. C. Solomon, Chem. Sci., 2019, 10, 4598 DOI: 10.1039/C8SC05464A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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