Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory

Jing Li (1) , Gabriele d'Avino (1) , Ivan Duchemin (2) , David Beljonne (3) , Xavier Blase (1)

1 NEEL - TMC - Théorie de la Matière Condensée
2 LSIM - Laboratory of Atomistic Simulation
3 UMons - Université de Mons

We present a novel hybrid quantum/classical approach to the calculation of charged excitations in molecular solids based on the many-body Green's function GW formalism. Molecules described at the GW level are embedded into the crystalline environment modeled with an accurate classical polarizable scheme. This allows the calculation of electron addition and removal energies in the bulk and at crystal surfaces where charged excitations are probed in photoelectron experiments. By considering the paradigmatic case of pentacene and perfluoropentacene crystals, we discuss the different contributions from intermolecular interactions to electronic energy levels, distinguishing between polarization, which is accounted for combining quantum and classical polarizabilities, and crystal field effects, that can impact energy levels by up to ±0.6 eV. After introducing band dispersion, we achieve quantitative agreement (within 0.2 eV) on the ionization potential and electron affinity measured at pentacene and perfluoropentacene crystal surfaces characterized by standing molecules.

Domaines: Chimie théorique et/ou physique; Science des matériaux [cond-mat.mtrl-sci]

Jing Li, Gabriele d'Avino, Ivan Duchemin, David Beljonne, Xavier Blase. Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory. Physical Review B, 2018, 97 (3), pp.035108. ⟨10.1103/PhysRevB.97.035108⟩. ⟨hal-01715820⟩