Understanding the Charge Transfer at the Interface of Electron Donors and Acceptors: TTF-TCNQ as an Example

Changwon Park; Viktor Atalla; Sean Smith; Mina Yoon

doi:10.1021/acsami.7b04148

Understanding the Charge Transfer at the Interface of Electron Donors and Acceptors: TTF-TCNQ as an Example

Changwon Park, Viktor Atalla, Sean Smith, Mina Yoon

Microstructural Evolution Modeling

Research output: Contribution to journal › Article › peer-review

20 Scopus citations

Abstract

Charge transfer between an electron donor and an electron acceptor is widely accepted as being independent of their relative configurations if the interaction between them is weak; however, the limit of this concept for an interacting system has not yet been well established. Our study of prototypical electron donor-acceptor molecules, tetrathiafulvalene-tetracyanoquinodimethane, using density functional theory based on an advanced functional, clearly demonstrates that for interacting molecules, their configurational arrangement is as important as their individual electronic properties in the asymptotic limit to determine the charge transfer direction. For the first time, we demonstrate that by changing their relative orientation, one can reverse the charge transfer direction of the pair, causing the molecules to exchange roles as donor and acceptor. Our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.

Original language	English
Pages (from-to)	27266-27272
Number of pages	7
Journal	ACS Applied Materials and Interfaces
Volume	9
Issue number	32
DOIs	https://doi.org/10.1021/acsami.7b04148
State	Published - Aug 16 2017

Funding

We acknowledge M. Scheffler for comments on the manuscript. This work was supported at the Center for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory (ORNL) by the Scientific User Facilities Division Office of Basic Energy Sciences, U.S. Department of Energy. Research (charge transfer analysis by C.P.) was partly supported by Creative Materials Discovery Program (2015M3D1A1070639), by Basic Science Research Program (NRF-2016R1D1A3B03933785) through the National Research Foundation of Korea (NRF) funding. Research (XC functional dependence analysis by V.A. and M.Y.) sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle LLC, for the U. S. Department of Energy. In addition, this work used computing resources at the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Funders	Funder number
Center for Nanophase Materials Sciences
Creative Materials Discovery Program	NRF-2016R1D1A3B03933785, 2015M3D1A1070639
Scientific User Facilities Division Office of Basic Energy Sciences
U.S. Department of Energy
Office of Science	DE-AC02-05CH11231
Oak Ridge National Laboratory
UT-Battelle
National Research Foundation of Korea

Keywords

TTF-TCNQ
charge transfer
density functional theory
electron donor-acceptor molecules
hybrid functional
interface phenomena

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10.1021/acsami.7b04148

Cite this

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abstract = "Charge transfer between an electron donor and an electron acceptor is widely accepted as being independent of their relative configurations if the interaction between them is weak; however, the limit of this concept for an interacting system has not yet been well established. Our study of prototypical electron donor-acceptor molecules, tetrathiafulvalene-tetracyanoquinodimethane, using density functional theory based on an advanced functional, clearly demonstrates that for interacting molecules, their configurational arrangement is as important as their individual electronic properties in the asymptotic limit to determine the charge transfer direction. For the first time, we demonstrate that by changing their relative orientation, one can reverse the charge transfer direction of the pair, causing the molecules to exchange roles as donor and acceptor. Our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.",

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AB - Charge transfer between an electron donor and an electron acceptor is widely accepted as being independent of their relative configurations if the interaction between them is weak; however, the limit of this concept for an interacting system has not yet been well established. Our study of prototypical electron donor-acceptor molecules, tetrathiafulvalene-tetracyanoquinodimethane, using density functional theory based on an advanced functional, clearly demonstrates that for interacting molecules, their configurational arrangement is as important as their individual electronic properties in the asymptotic limit to determine the charge transfer direction. For the first time, we demonstrate that by changing their relative orientation, one can reverse the charge transfer direction of the pair, causing the molecules to exchange roles as donor and acceptor. Our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.

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Understanding the Charge Transfer at the Interface of Electron Donors and Acceptors: TTF-TCNQ as an Example

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