Hydrogen bonding as the origin of the switching behavior in dithiolated phenylene-vinylene oligomers

Handle URI:
http://hdl.handle.net/10754/315779
Title:
Hydrogen bonding as the origin of the switching behavior in dithiolated phenylene-vinylene oligomers
Authors:
Obodo, Tobechukwu Joshua ( 0000-0003-1511-0918 ) ; Gkionis, Konstantinos; Rungger, Ivan; Sanvito, Stefano; Schwingenschlögl, Udo ( 0000-0003-4179-7231 )
Abstract:
We investigate theoretically the switching behavior of a dithiolated phenylene-vinylene oligomer sandwiched between Au(111) electrodes using self-interaction corrected density-functional theory combined with the nonequilibrium Green's-function method for quantum transport. The molecule presents a configurational bistability, which can be exploited in constructing molecular memories, switches, and sensors. We find that protonation of the terminating thiol groups is at the origin of the change in conductance. H bonding at the thiol group weakens the S-Au bond and reduces by about one order of magnitude the transmission coefficient at the Fermi level, and thus the linear response conductance. Furthermore, protonation downshifts in energy the position of the highest occupied molecular orbital, so that the current of the protonated species is lower than that of the unprotonated one along the entire bias range investigated, from −1.5 to 1.5 V. A second protonation at the opposite thiol group has only minor effects and no further drastic reduction in transmission takes place. Our results allow us to re-interpret the experimental data originally attributing the conductance reduction to H dissociation.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Computational Physics and Materials Science (CPMS)
Citation:
Obodo JT, Gkionis K, Rungger I, Sanvito S, Schwingenschlögl U (2013) Hydrogen bonding as the origin of the switching behavior in dithiolated phenylene-vinylene oligomers. Phys Rev B 88. doi:10.1103/PhysRevB.88.085438.
Publisher:
American Physical Society
Journal:
Physical Review B
Issue Date:
29-Aug-2013
DOI:
10.1103/PhysRevB.88.085438
Type:
Article
ISSN:
1098-0121; 1550-235X
Additional Links:
http://link.aps.org/doi/10.1103/PhysRevB.88.085438
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Computational Physics and Materials Science (CPMS)

Full metadata record

DC FieldValue Language
dc.contributor.authorObodo, Tobechukwu Joshuaen
dc.contributor.authorGkionis, Konstantinosen
dc.contributor.authorRungger, Ivanen
dc.contributor.authorSanvito, Stefanoen
dc.contributor.authorSchwingenschlögl, Udoen
dc.date.accessioned2014-04-13T14:33:32Z-
dc.date.available2014-04-13T14:33:32Z-
dc.date.issued2013-08-29en
dc.identifier.citationObodo JT, Gkionis K, Rungger I, Sanvito S, Schwingenschlögl U (2013) Hydrogen bonding as the origin of the switching behavior in dithiolated phenylene-vinylene oligomers. Phys Rev B 88. doi:10.1103/PhysRevB.88.085438.en
dc.identifier.issn1098-0121en
dc.identifier.issn1550-235Xen
dc.identifier.doi10.1103/PhysRevB.88.085438en
dc.identifier.urihttp://hdl.handle.net/10754/315779en
dc.description.abstractWe investigate theoretically the switching behavior of a dithiolated phenylene-vinylene oligomer sandwiched between Au(111) electrodes using self-interaction corrected density-functional theory combined with the nonequilibrium Green's-function method for quantum transport. The molecule presents a configurational bistability, which can be exploited in constructing molecular memories, switches, and sensors. We find that protonation of the terminating thiol groups is at the origin of the change in conductance. H bonding at the thiol group weakens the S-Au bond and reduces by about one order of magnitude the transmission coefficient at the Fermi level, and thus the linear response conductance. Furthermore, protonation downshifts in energy the position of the highest occupied molecular orbital, so that the current of the protonated species is lower than that of the unprotonated one along the entire bias range investigated, from −1.5 to 1.5 V. A second protonation at the opposite thiol group has only minor effects and no further drastic reduction in transmission takes place. Our results allow us to re-interpret the experimental data originally attributing the conductance reduction to H dissociation.en
dc.language.isoenen
dc.publisherAmerican Physical Societyen
dc.relation.urlhttp://link.aps.org/doi/10.1103/PhysRevB.88.085438en
dc.rightsArchived with thanks to Physical Review Ben
dc.titleHydrogen bonding as the origin of the switching behavior in dithiolated phenylene-vinylene oligomersen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentComputational Physics and Materials Science (CPMS)en
dc.identifier.journalPhysical Review Ben
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionSchool of Physics and CRANN, Trinity College, Dublin 2, Irelanden
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorGkionis, Konstantinosen
kaust.authorSchwingenschlögl, Udoen
kaust.authorObodo, Tobechukwu Joshuaen
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