Interference-induced electron- and hole-conduction asymmetry

Wohlthat, S; Solomon, GC; Hush, NS; Reimers, JR

Interference-induced electron- and hole-conduction asymmetry

Wohlthat, S Solomon, GC Hush, NS Reimers, JR

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Publication Type:: Journal Article
Citation:: Theoretical Chemistry Accounts, 2011, 130 (4-6), pp. 815 - 828
Issue Date:: 2011-12-01

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Field	Value	Language
dc.contributor.author	Wohlthat, S	en_US
dc.contributor.author	Solomon, GC	en_US
dc.contributor.author	Hush, NS	en_US
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.date.issued	2011-12-01	en_US
dc.identifier.citation	Theoretical Chemistry Accounts, 2011, 130 (4-6), pp. 815 - 828	en_US
dc.identifier.issn	1432-881X	en_US
dc.identifier.uri	http://hdl.handle.net/10453/28186
dc.description.abstract	Principles established by Shephard and Paddon-Row for optimizing and controlling intramolecular electron transport through the modulation of interfering pathways are employed to design new molecules for steady-state conduction experiments aimed at manifesting electron-hole conduction asymmetry in a unique way. First, a review of the basic principles is presented through application to a pertinent model system in which a molecule containing donor and acceptor terminal linking groups with an internal multiple-pathway bridge is used to span two metal electrodes. Different interference patterns are produced depending on whether the through-molecule coupling pathways are symmetric or antisymmetric with respect to a topological bisecting plane, giving rise to asymmetric electron and hole conductances at the tight-binding (Hückel) level; this process is also described from a complementary molecular-orbital viewpoint. Subsequently, a new molecular system based on organic polyradicals is designed to allow such asymmetry to be realized in single-molecule conduction experiments. These polyradicals are analyzed using analogous simple models, density-functional theory (DFT) calculations of steady-state transmission, and intermediate neglect of differential overlap (INDO) calculations of intramolecular connectivity, verifying that polyradicals at low temperatures should show experimentally measureable electron-hole conduction asymmetry. A key feature of this system is that the polyradicals form a narrow partially occupied band of orbitals that lie within and well separated from the HOMO and LUMO orbitals of the surrounding molecular scaffold, allowing for holes and electrons to be transported through the same molecular band. © 2011 Springer-Verlag.	en_US
dc.relation.ispartof	Theoretical Chemistry Accounts	en_US
dc.relation.isbasedon	10.1007/s00214-011-1045-2	en_US
dc.subject.classification	Chemical Physics	en_US
dc.title	Interference-induced electron- and hole-conduction asymmetry	en_US
dc.type	Journal Article
utslib.citation.volume	4-6	en_US
utslib.citation.volume	130	en_US
utslib.for	0307 Theoretical and Computational Chemistry	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
utslib.copyright.status	closed_access
pubs.issue	4-6	en_US
pubs.publication-status	Published	en_US
pubs.volume	130	en_US

Abstract:

Principles established by Shephard and Paddon-Row for optimizing and controlling intramolecular electron transport through the modulation of interfering pathways are employed to design new molecules for steady-state conduction experiments aimed at manifesting electron-hole conduction asymmetry in a unique way. First, a review of the basic principles is presented through application to a pertinent model system in which a molecule containing donor and acceptor terminal linking groups with an internal multiple-pathway bridge is used to span two metal electrodes. Different interference patterns are produced depending on whether the through-molecule coupling pathways are symmetric or antisymmetric with respect to a topological bisecting plane, giving rise to asymmetric electron and hole conductances at the tight-binding (Hückel) level; this process is also described from a complementary molecular-orbital viewpoint. Subsequently, a new molecular system based on organic polyradicals is designed to allow such asymmetry to be realized in single-molecule conduction experiments. These polyradicals are analyzed using analogous simple models, density-functional theory (DFT) calculations of steady-state transmission, and intermediate neglect of differential overlap (INDO) calculations of intramolecular connectivity, verifying that polyradicals at low temperatures should show experimentally measureable electron-hole conduction asymmetry. A key feature of this system is that the polyradicals form a narrow partially occupied band of orbitals that lie within and well separated from the HOMO and LUMO orbitals of the surrounding molecular scaffold, allowing for holes and electrons to be transported through the same molecular band. © 2011 Springer-Verlag.

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http://hdl.handle.net/10453/28186