title: Controlling the rectification properties of molecular junctions through molecule-electrode coupling.
abstract: The development of molecular components functioning as switches, rectifiers or amplifiers is a great challenge in molecular electronics. A desirable property of such components is functional robustness, meaning that the intrinsic functionality of components must be preserved regardless of the strategy used to integrate them into the final assemblies. Here, this issue is investigated for molecular diodes based on N-phenylbenzamide (NPBA) backbones. The transport properties of molecular junctions derived from NPBA are characterized while varying the nature of the functional groups interfacing the backbone and the gold electrodes required for break-junction measurements. Combining experimental and theoretical methods, it is shown that at low bias (<0.85 V) transport is determined by the same frontier molecular orbital originating from the NPBA core, regardless of the anchoring group employed. The magnitude of rectification, however, is strongly dependent on the strength of the electronic coupling at the gold-NPBA interface and on the spatial distribution of the local density of states of the dominant transport channel of the molecular junction.
authors.affiliation: Department of Chemistry & Energy Sciences Institute, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA. gary.brudvig@yale.edu victor.batisa@yale.edu charles.schmuttenmaer@yale.edu robert.crabtree@yale.edu.
authors.forename: Matthieu
authors.initials: M
authors.lastname: Koepf
authors.affiliation: Department of Chemistry & Energy Sciences Institute, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA. gary.brudvig@yale.edu victor.batisa@yale.edu charles.schmuttenmaer@yale.edu robert.crabtree@yale.edu.
authors.forename: Christopher
authors.initials: C
authors.lastname: Koenigsmann
authors.affiliation: Department of Chemistry & Energy Sciences Institute, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA. gary.brudvig@yale.edu victor.batisa@yale.edu charles.schmuttenmaer@yale.edu robert.crabtree@yale.edu.
authors.forename: Wendu
authors.identifier: http://orcid.org/0000-0002-5365-7060
authors.initials: W
authors.lastname: Ding
authors.affiliation: Department of Applied Physics and Applied Mathematics, Columbia University, Mail Code: 4701, New York, NY 10027, USA. lv2117@columbia.edu.
authors.forename: Arunbah
authors.initials: A
authors.lastname: Batra
authors.affiliation: Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors.forename: Christian F A
authors.initials: CF
authors.lastname: Negre
authors.affiliation: Department of Applied Physics and Applied Mathematics, Columbia University, Mail Code: 4701, New York, NY 10027, USA. lv2117@columbia.edu.
authors.forename: Latha
authors.initials: L
authors.lastname: Venkataraman
authors.affiliation: Department of Chemistry & Energy Sciences Institute, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA. gary.brudvig@yale.edu victor.batisa@yale.edu charles.schmuttenmaer@yale.edu robert.crabtree@yale.edu.
authors.forename: Gary W
authors.initials: GW
authors.lastname: Brudvig
authors.affiliation: Department of Chemistry & Energy Sciences Institute, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA. gary.brudvig@yale.edu victor.batisa@yale.edu charles.schmuttenmaer@yale.edu robert.crabtree@yale.edu.
authors.forename: Victor S
authors.initials: VS
authors.lastname: Batista
authors.affiliation: Department of Chemistry & Energy Sciences Institute, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA. gary.brudvig@yale.edu victor.batisa@yale.edu charles.schmuttenmaer@yale.edu robert.crabtree@yale.edu.
authors.forename: Charles A
authors.initials: CA
authors.lastname: Schmuttenmaer
authors.affiliation: Department of Chemistry & Energy Sciences Institute, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA. gary.brudvig@yale.edu victor.batisa@yale.edu charles.schmuttenmaer@yale.edu robert.crabtree@yale.edu.
authors.forename: Robert H
authors.initials: RH
authors.lastname: Crabtree