Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer

Reslan, Randa; Lopata, Kenneth; Arntsen, Christopher; Govind, Niranjan; Neuhauser, Daniel

doi:10.1063/1.4729047

Title: Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer

Journal Article · Fri Dec 14 00:00:00 EST 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4729047· OSTI ID:1386642

Reslan, Randa; Lopata, Kenneth; Arntsen, Christopher; Govind, Niranjan; Neuhauser, Daniel

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.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Molecularly Engineered Energy Materials (MEEM)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: SC0001342

OSTI ID:: 1386642

Journal Information:: Journal of Chemical Physics, Vol. 137, Issue 22; Related Information: MEEM partners with University of California, Los Angeles (lead); University of California, Berkeley; Eastern Washington University; University of Kansas; National Renewable Energy Laboratory; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

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