Modeling the Photochrome–TiO 2 Interface with Bethe–Salpeter and Time-Dependent Density Functional Theory Methods

Daniel Escudero (1) , Ivan Duchemin (2) , Xavier Blase (3) , Denis Jacquemin (1)

1 CEISAM - Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation
2 LSIM - Laboratory of Atomistic Simulation
3 NEEL - TMC - Théorie de la Matière Condensée

Hybrid organic–inorganic semiconductor systems have important applications in both molecular electronics and photoresponsive materials. The characterizations of the interface and of the electronic excited-states of these hybrid systems remain a challenge for state-of-the-art computational methods, as the systems of interest are large. In the present investigation, we present for the first time a many-body Green’s function Bethe–Salpeter investigation of a series of photochromic molecules adsorbed onto TiO2 nanoclusters. On the basis of these studies, the performance of time-dependent density functional theory (TD-DFT) calculations is assessed. In addition, the photochromic properties of different hybrid systems are also evaluated. This work shows that qualitatively different conclusions can be reached with TD-DFT relying on various exchange–correlation functionals for such organic–inorganic interfaces and paves the way to more accurate simulation of many hybrid materials.

Mots clés: TD-DFT; BSE/GW; exchange-correlation functionals; photochromes; azobenzene; hybrid organic/inorganic systems; interface

Domaines: Chimie théorique et/ou physique; Electronique

Daniel Escudero, Ivan Duchemin, Xavier Blase, Denis Jacquemin. Modeling the Photochrome–TiO 2 Interface with Bethe–Salpeter and Time-Dependent Density Functional Theory Methods. Journal of Physical Chemistry Letters, 2017, 8 (5), pp.936 - 940. ⟨10.1021/acs.jpclett.7b00015⟩. ⟨hal-01625569⟩