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 dimers. 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.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1061409
- Report Number(s):
- PNNL-SA-86069; 42591; KP1704020
- Journal Information:
- Journal of Chemical Physics, 137(22):Article No. 22A502, Journal Name: Journal of Chemical Physics, 137(22):Article No. 22A502
- Country of Publication:
- United States
- Language:
- English
Similar Records
Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer
Excited-state studies of polyacenes: A comparative picture using EOMCCSD, CR-EOMCCSD(T), range-separated (LR/RT)-TDDFT, TD-PM3 and TD-ZINDO