title: Computational Design of Intrinsic Molecular Rectifiers Based on Asymmetric Functionalization of N-Phenylbenzamide.
abstract: We report a systematic computational search of molecular frameworks for intrinsic rectification of electron transport. The screening of molecular rectifiers includes 52 molecules and conformers spanning over 9 series of structural motifs. N-Phenylbenzamide is found to be a promising framework with both suitable conductance and rectification properties. A targeted screening performed on 30 additional derivatives and conformers of N-phenylbenzamide yielded enhanced rectification based on asymmetric functionalization. We demonstrate that electron-donating substituent groups that maintain an asymmetric distribution of charge in the dominant transport channel (e.g., HOMO) enhance rectification by raising the channel closer to the Fermi level. These findings are particularly valuable for the design of molecular assemblies that could ensure directionality of electron transport in a wide range of applications, from molecular electronics to catalytic reactions.
authors.affiliation: Department of Chemistry, Yale University , P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.|Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
authors.forename: Wendu
authors.initials: W
authors.lastname: Ding
authors.affiliation: Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
authors.forename: Matthieu
authors.initials: M
authors.lastname: Koepf
authors.affiliation: Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
authors.forename: Christopher
authors.initials: C
authors.lastname: Koenigsmann
authors.affiliation: Department of Applied Physics and Applied Mathematics, Columbia University , New York, New York 10027, United States.
authors.forename: Arunabh
authors.initials: A
authors.lastname: Batra
authors.affiliation: Department of Applied Physics and Applied Mathematics, Columbia University , New York, New York 10027, United States.
authors.forename: Latha
authors.initials: L
authors.lastname: Venkataraman
authors.affiliation: Department of Chemistry, Yale University , P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.|Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
authors.forename: Christian F A
authors.initials: CF
authors.lastname: Negre
authors.affiliation: Department of Chemistry, Yale University , P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.|Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
authors.forename: Gary W
authors.initials: GW
authors.lastname: Brudvig
authors.affiliation: Department of Chemistry, Yale University , P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.|Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
authors.forename: Robert H
authors.initials: RH
authors.lastname: Crabtree
authors.affiliation: Department of Chemistry, Yale University , P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.|Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
authors.forename: Charles A
authors.initials: CA
authors.lastname: Schmuttenmaer
authors.affiliation: Department of Chemistry, Yale University , P.O. Box 208107, New Haven, Connecticut 06520-8107, United States.|Yale Energy Sciences Institute, Yale University , P.O. Box 27394, West Haven, Connecticut 06516-7394, United States.
authors.forename: Victor S
authors.initials: VS
authors.lastname: Batista