title: Electrostatic Embedding To Model the Impact of Environment on Photophysical Properties of Molecular Crystals: A Self-Consistent Charge Adjustment Procedure.
abstract: A case study of 1,8-dihydroxy-2-napthaldehyde (DHNA)-exhibiting an excited-state intramolecular double proton transfer resulting in photophysical properties sensitive to the surrounding environment-has been used to assess the performance of electrostatic embedding approaches designed to accurately recover the effects of a bulk crystalline environment on calculated photophysical properties. The first approach, based on time-dependent density functional theory (TD-DFT) applied in a QM/QM' scheme, makes use of a background point charge distribution which can accurately reproduce the exact ground-state Ewald potential of the bulk crystal. The second approach seeks to "optimize" these charges in a self-consistent manner in order to reproduce the electrostatic field produced by the environment at the excited state. Using these two approaches, both absorption and emission properties of molecular crystals, such as the position and the relative shift in the emission bands in the solid state with respect to solution, can be accurately reproduced. More generally, the results obtained show how these computationally affordable approaches can be used to predict the excited-state behavior of molecules in condensed phases, thus allowing their employment to predict or design new molecular materials with enhanced photophysical properties.
authors.affiliation: PSL Research University , Institut de Recherche de Chimie Paris IRCP, CNRS-Chimie ParisTech, 11 rue Pierre et Marie Curie, F-75005 Paris, France.
authors.forename: Liam
authors.initials: L
authors.lastname: Wilbraham
authors.affiliation: PSL Research University , Institut de Recherche de Chimie Paris IRCP, CNRS-Chimie ParisTech, 11 rue Pierre et Marie Curie, F-75005 Paris, France.|Institut Universitaire de France , 103 Boulevard Saint Michel, F-75005 Paris, France.
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo
authors.affiliation: PSL Research University , Institut de Recherche de Chimie Paris IRCP, CNRS-Chimie ParisTech, 11 rue Pierre et Marie Curie, F-75005 Paris, France.
authors.forename: Frédéric
authors.initials: F
authors.lastname: Labat
authors.affiliation: PSL Research University , Institut de Recherche de Chimie Paris IRCP, CNRS-Chimie ParisTech, 11 rue Pierre et Marie Curie, F-75005 Paris, France.
authors.forename: Ilaria
authors.initials: I
authors.lastname: Ciofini