TY  - JOUR
A1  - Sutton, Christopher
A1  - Körzdörfer, Thomas
A1  - Coropceanu, Veaceslav
A1  - Bredas, Jean-Luc
T1  - Toward a robust quantum-chemical description of organic mixed-valence systems
JF  - The journal of physical chemistry : C, Nanomaterials and interfaces
N2  - The electronic coupling between redox sites in mixed-valence systems has attracted the interest of the chemistry community for a long time. Many computational studies have focused on trying to determine its magnitude as a function of the nature of the redox sites and of the bridge(s) between them. However, in most instances, the quantum-chemical methodologies that have been employed suffer from intrinsic errors that lead to either an overlocalized or an overdelocalized character of the electronic structure. These deficiencies prevent an accurate depiction of the degree of charge (de)localization in the system and, as a result, of the extent of electronic coupling. Here we use nonempirically tuned long-range corrected density functional theory and show that it provides a robust, efficient approach to characterize organic mixed-valence systems. We first demonstrate the performance of this approach via a study of representative Robin-Day class-II (localized) and class-III (delocalized) complexes. We then examine a borderline class-II/class-III complex, which had proven difficult to describe accurately with standard density functional theory and Hartree-Fock methods.
Y1  - 2014
U6  - https://doi.org/10.1021/jp410461v
SN  - 1932-7447
VL  - 118
IS  - 8
SP  - 3925
EP  - 3934
PB  - American Chemical Society
CY  - Washington
ER  -