title: Estimation of π-π Electronic Couplings from Current Measurements.
abstract: The π-π interactions between organic molecules are among the most important parameters for optimizing the transport and optical properties of organic transistors, light-emitting diodes, and (bio-) molecular devices. Despite substantial theoretical progress, direct experimental measurement of the π-π electronic coupling energy parameter t has remained an old challenge due to molecular structural variability and the large number of parameters that affect the charge transport. Here, we propose a study of π-π interactions from electrochemical and current measurements on a large array of ferrocene-thiolated gold nanocrystals. We confirm the theoretical prediction that t can be assessed from a statistical analysis of current histograms. The extracted value of t ≈35 meV is in the expected range based on our density functional theory analysis. Furthermore, the t distribution is not necessarily Gaussian and could be used as an ultrasensitive technique to assess intermolecular distance fluctuation at the subangström level. The present work establishes a direct bridge between quantum chemistry, electrochemistry, organic electronics, and mesoscopic physics, all of which were used to discuss results and perspectives in a quantitative manner.
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology, CNRS, University of Lille , Avenue Poincaré, BP60069, 59652, Villeneuve d'Ascq France.
authors.forename: J
authors.initials: J
authors.lastname: Trasobares
authors.affiliation: Aix Marseille University, Universite de Toulon, CNRS, CPT , 163 Avenue de Luminy, 13288 Marseille cedex 9, France.
authors.forename: J
authors.initials: J
authors.lastname: Rech
authors.affiliation: Aix Marseille University, Universite de Toulon, CNRS, CPT , 163 Avenue de Luminy, 13288 Marseille cedex 9, France.
authors.forename: T
authors.initials: T
authors.lastname: Jonckheere
authors.affiliation: Aix Marseille University, Universite de Toulon, CNRS, CPT , 163 Avenue de Luminy, 13288 Marseille cedex 9, France.
authors.forename: T
authors.initials: T
authors.lastname: Martin
authors.affiliation: Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou , 2 bd Lavoisier, 49045 Angers cedex, France.
authors.forename: O
authors.initials: O
authors.lastname: Aleveque
authors.affiliation: Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou , 2 bd Lavoisier, 49045 Angers cedex, France.
authors.forename: E
authors.initials: E
authors.lastname: Levillain
authors.affiliation: Laboratory for Chemistry of Novel Materials, University of Mons , Place du Parc 20, B-7000 Mons, Belgium.
authors.forename: V
authors.initials: V
authors.lastname: Diez-Cabanes
authors.affiliation: Laboratory for Chemistry of Novel Materials, University of Mons , Place du Parc 20, B-7000 Mons, Belgium.
authors.forename: Y
authors.initials: Y
authors.lastname: Olivier
authors.affiliation: Laboratory for Chemistry of Novel Materials, University of Mons , Place du Parc 20, B-7000 Mons, Belgium.
authors.forename: J
authors.initials: J
authors.lastname: Cornil
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology, CNRS, University of Lille , Avenue Poincaré, BP60069, 59652, Villeneuve d'Ascq France.
authors.forename: J P
authors.initials: JP
authors.lastname: Nys
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology, CNRS, University of Lille , Avenue Poincaré, BP60069, 59652, Villeneuve d'Ascq France.
authors.forename: R
authors.initials: R
authors.lastname: Sivakumarasamy
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology, CNRS, University of Lille , Avenue Poincaré, BP60069, 59652, Villeneuve d'Ascq France.
authors.forename: K
authors.initials: K
authors.lastname: Smaali
authors.affiliation: Laboratory for Chemistry of Novel Materials, University of Mons , Place du Parc 20, B-7000 Mons, Belgium.
authors.forename: P
authors.initials: P
authors.lastname: Leclere
authors.affiliation: NTT Basic Research Laboratories, 3-1, Morinosato Wakamiya, Atsugi-shi, kanagawa 243-0198, Japan.
authors.forename: A
authors.initials: A
authors.lastname: Fujiwara
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology, CNRS, University of Lille , Avenue Poincaré, BP60069, 59652, Villeneuve d'Ascq France.
authors.forename: D
authors.initials: D
authors.lastname: Théron
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology, CNRS, University of Lille , Avenue Poincaré, BP60069, 59652, Villeneuve d'Ascq France.
authors.forename: D
authors.identifier: 0000-0002-3362-1669
authors.initials: D
authors.lastname: Vuillaume
authors.affiliation: Institute of Electronics, Microelectronics and Nanotechnology, CNRS, University of Lille , Avenue Poincaré, BP60069, 59652, Villeneuve d'Ascq France.|NTT Basic Research Laboratories, 3-1, Morinosato Wakamiya, Atsugi-shi, kanagawa 243-0198, Japan.
authors.forename: N
authors.identifier: 0000-0002-4924-4087
authors.initials: N
authors.lastname: Clément
keywords: Cooperative effect; coupled quantum dot; molecular electronics; nanoelectrochemistry; transfer integral; π−π interaction