title: Electron-flux infrared response to varying π-bond topology in charged aromatic monomers.
abstract: The interaction of delocalized π-electrons with molecular vibrations is key to charge transport processes in π-conjugated organic materials based on aromatic monomers. Yet the role that specific aromatic motifs play on charge transfer is poorly understood. Here we show that the molecular edge topology in charged catacondensed aromatic hydrocarbons influences the Herzberg-Teller coupling of π-electrons with molecular vibrations. To this end, we probe the radical cations of picene and pentacene with benchmark armchair- and zigzag-edges using infrared multiple-photon dissociation action spectroscopy and interpret the recorded spectra via quantum-chemical calculations. We demonstrate that infrared bands preserve information on the dipolar π-electron-flux mode enhancement, which is governed by the dynamical evolution of vibronically mixed and correlated one-electron configuration states. Our results reveal that in picene a stronger charge π-flux is generated than in pentacene, which could justify the differences of electronic properties of armchair- versus zigzag-type families of technologically relevant organic molecules.
authors: Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098XH Amsterdam, The Netherlands.
authors: Héctor
authors: H
authors: Álvaro Galué
authors: Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098XH Amsterdam, The Netherlands.|Radboud University, Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7, 6525ED Nijmegen, The Netherlands.
authors: Jos
authors: J
authors: Oomens
authors: Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098XH Amsterdam, The Netherlands.
authors: Wybren Jan
authors: http://orcid.org/0000-0002-1265-8016
authors: WJ
authors: Buma
authors: Radboud University, Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7, 6525ED Nijmegen, The Netherlands.
authors: Britta
authors: B
authors: Redlich