Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer
We use time-dependent density functional theory and time-dependent ZINDO (a semi-empirical method) to study transfer of an extra electron between a pair of pentacene molecules. A measure of the electronic transfer integral is computed in a dynamic picture via the vertical excitation energy from a delocalized anionic ground state. With increasing dimer separation, this dynamical measurement of charge transfer is shown to be significantly larger than the commonly used static approximation (i.e., LUMO+1-LUMO of the neutral dimer, or HOMO-LUMO of the charged dimer), up to an order of magnitude higher at 6 Å. These results offer a word of caution for calculations involving large separations, as in organic photovoltaics, where care must be taken when using a static picture to model charge transfer. © 2012 American Institute of Physics.
Publication Source (Journal or Book title)
Journal of Chemical Physics
Reslan, R., Lopata, K., Arntsen, C., Govind, N., & Neuhauser, D. (2012). Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer. Journal of Chemical Physics, 137 (22) https://doi.org/10.1063/1.4729047