title: Combining the Many-Body GW Formalism with Classical Polarizable Models: Insights on the Electronic Structure of Molecular Solids.
abstract: We present an original hybrid QM/MM scheme merging the many-body Green's function GW formalism with classical discrete polarizable models and its application to the paradigmatic case of a pentacene crystal. Our calculated transport gap is found to be in excellent agreement with reference periodic bulk GW calculations, together with properly parametrized classical microelectrostatic calculations, and with photoionization measurements at crystal surfaces. More importantly, we prove that the gap is insensitive to the partitioning of pentacene molecules in QM and MM subsystems, as a result of the mutual compensation of quantum and classical polarizabilities, clarifying the relation between polarization energy and delocalization. The proposed hybrid method offers a computationally attractive strategy to compute the full spectrum of charged excitations in complex molecular environments, accounting for both QM and MM contributions to the polarization energy, a crucial requirement in the limit of large QM subsystems.
authors.affiliation: Grenoble Alpes University, CNRS, Institut NÉEL , F-38042 Grenoble, France.
authors.forename: Jing
authors.initials: J
authors.lastname: Li
authors.affiliation: Laboratory for Chemistry of Novel Materials, University of Mons , Place du Parc 20, BE-7000 Mons, Hainaut, Belgium.
authors.forename: Gabriele
authors.initials: G
authors.lastname: D'Avino
authors.affiliation: INAC, SP2M/L_Sim, CEA/UJF , Cedex 09, 38054 Grenoble, France.
authors.forename: Ivan
authors.initials: I
authors.lastname: Duchemin
authors.affiliation: Laboratory for Chemistry of Novel Materials, University of Mons , Place du Parc 20, BE-7000 Mons, Hainaut, Belgium.
authors.forename: David
authors.initials: D
authors.lastname: Beljonne
authors.affiliation: Grenoble Alpes University, CNRS, Institut NÉEL , F-38042 Grenoble, France.
authors.forename: Xavier
authors.initials: X
authors.lastname: Blase