title: Ab Initio Modeling of Donor-Acceptor Interactions and Charge-Transfer Excitations in Molecular Complexes: The Case of Terthiophene-Tetracyanoquinodimethane.
abstract: This work presents a thorough quantum chemical study of the terthiophene-tetracyanoquinodimethane complex as a model for π-π donor-acceptor systems. Dispersion-corrected hybrid (B3LYP-D) and double hybrid (B2PLYP-D), hybrid meta (M06-2X and M06-HF), and recently proposed long-range corrected (LC-wPBE, CAM-B3LYP, and wB97X-D) functionals have been chosen to deal with π-π intermolecular interactions and charge-transfer excitations in a balanced way. These properties are exhaustively compared to those computed with high-level ab initio SCS-MP2 and CASPT2 methods. The wB97X-D functional exhibits the best performance. It provides reliable intermolecular distances and interaction energies and predicts a small charge transfer from the donor to the acceptor in the ground state. In addition, wB97X-D is also able to yield an accurate description of the charge-transfer excitations in comparison to benchmark CASPT2 calculations.
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia , E-46980 Valencia, Spain.|Laboratory for Chemistry of Novel Materials, Université de Mons , Place du Parc 20, B-7000 Mons, Belgium.
authors.forename: Juan
authors.initials: J
authors.lastname: Aragó
authors.affiliation: Departamento de Química Física, Universidad de Alicante , E-03080 Alicante, Spain.
authors.forename: Juan C
authors.initials: JC
authors.lastname: Sancho-García
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia , E-46980 Valencia, Spain.
authors.forename: Enrique
authors.initials: E
authors.lastname: Ortí
authors.affiliation: Laboratory for Chemistry of Novel Materials, Université de Mons , Place du Parc 20, B-7000 Mons, Belgium.
authors.forename: David
authors.initials: D
authors.lastname: Beljonne