Correction: Helical orbitals and circular currents in linear carbon wires

Garner, Marc H.; Jensen, Annie Aarup; Hyllested, Louise O. H.; Solomon, Gemma C.

doi:10.1039/d0sc90031a

Cited by 1 publication

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“…However, we recently demonstrated that the electronic transmission through even- n cumulenes can be almost as high as that of the equivalent odd- n systems by splitting the helical frontier molecular orbitals using pyramidalized π-donor substituents. Strategies for manipulating the helical electronic structure of cumulenes using substituents is described in detail elsewhere. ,,− …”

Section: Results: Even-n Cumulenic Carbon Wiresmentioning

confidence: 99%

“…Strategies for manipulating the helical electronic structure of cumulenes using substituents is described in detail elsewhere. [39][40][45][46][47] ELECTRONIC STRUCTURE. The four frontier molecular orbitals and their eigenvalues are calculated for the [4]cumulene-SMe in Figure 8.…”

Section: Even-n Cumulenic Carbon Wiresmentioning

confidence: 99%

“…39 In the molecular orbital picture, the possibility of electronic coupling between perpendicular end-groups of an sp-hybridized carbon wire manifests itself in the form of helical molecular orbitals that span the entire length of the linear carbon bridge. [39][40][41][42][43][44][45][46][47] Such helical p-orbitals appear in linear carbon wires upon a suitable reduction of symmetry due to substituents or axial torsion.…”

Section: Introductionmentioning

confidence: 99%

“…[48][49][50][51][52][53][54] Despite having perpendicular end-groups in their ground-state structure, odd-carbon cumulenes with pyramidalized single-faced p-donor substituents can achieve high electronic transmission similar to that of even-carbon cumulenes and polyynes. [45][46]55 Furthermore, helical p-orbitals can give rise to ring currents around the linear wire where the circular direction of the current is controlled by the helicity of the frontier orbitals. The understanding of the relation between helical molecular orbitals, electronic transmission, and ring currents in linear systems is still in its infancy.…”

Section: Introductionmentioning

confidence: 99%

“…In the molecular orbital picture, the possibility of electronic coupling between perpendicular end-groups of an sp-hybridized carbon wire manifests itself in the form of helical molecular orbitals that span the entire length of the linear carbon bridge. − Such helical π-orbitals appear in linear carbon wires upon a suitable reduction of symmetry due to substituents or axial torsion. Consequently, a molecule can be single-handed chiral while orbitals of both helicities appear; this has serendipitously been shown for a number of linear molecular systems. − Despite having perpendicular end-groups in their ground-state structure, odd-carbon cumulenes with pyramidalized single-faced π-donor substituents can achieve high electronic transmission similar to that of even-carbon cumulenes and polyynes. ,, Furthermore, helical π-orbitals can give rise to ring currents around the linear wire where the circular direction of the current is controlled by the helicity of the frontier orbitals. The understanding of the relation between helical molecular orbitals, electronic transmission, and ring currents in linear systems is still in its infancy. , Motivated by the insight local pictures of ballistic current provide for aromatic hydrocarbons, − we will address this issue further in this study.…”

Section: Introductionmentioning

confidence: 99%

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Three Distinct Torsion Profiles of Electronic Transmission through Linear Carbon Wires

2020

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The one-dimensional carbon allotrope carbyne, a linear chain of sp-hybridized carbon atoms, is predicted to exist in a polyynic and a cumulenic structure. While molecular forms of carbyne have been extensively characterized, the structural nature is hard to determine for many linear carbon wires that are made in-situ during pulling experiments. Here, we show that cumulenes and polyynes have distinctively different low-bias conductance profiles under axial torsion. We analyze the change of the electronic structure, Landauer transmission, and ballistic current density of the three types of closed-shell molecular carbynes as a function of the torsion angle. Both polyynic, odd-carbon cumulenic, and even-carbon cumulenic carbon wires exhibit helical frontier molecular orbitals when the end-groups are not in a co-planar configuration. This helical conjugation effect gives rise to strong ring current patterns around the linear wires. Only the transmission of even-carbon polyynic wires follows the well-known cosine-squared law with axial torsion that is also seen in biphenyl-type systems. Notably, the transmission of even-carbon cumulenic carbon wires rises with axial torsion from co-planar towards perpendicular orientation of the end-groups. The three distinct transmission profiles of polyynes, odd-carbon cumulenes, and even-carbon cumulenes may allow for experimental identification of the structural nature of linear carbon wires. Their different electron transport properties under axial torsion furthermore underline that, in the molecular limit of carbyne, three different subclasses of linear carbon wires exist. File list (3)download file view on ChemRxiv torsion_chemrxiv3.pdf (6.17 MiB) download file view on ChemRxiv SI_chemrxiv3.pdf (9.24 MiB) download file view on ChemRxiv files.zip (21.38 MiB)

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