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

Park, Changwon; Atalla, Viktor; Smith, Sean; Yoon, Mina

doi:10.1021/acsami.7b04148

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

Journal Article · Fri Jun 16 00:00:00 EDT 2017 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.7b04148· OSTI ID:1429209

^[1]; Atalla, Viktor ^[2]; Smith, Sean ^[3]; ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Fritz Haber Inst. of the Max Planck Society, Berlin (Germany)
Univ. of New South Wales, Sydney, NSW (Australia)

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. In conclusion, our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: National Research Foundation of Korea (NRF); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 1429209

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 32 Vol. 9; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (30)

Bonded-atom fragments for describing molecular charge densities Hirshfeld, F. L. Theoretica Chimica Acta, Vol. 44, Issue 2 https://doi.org/10.1007/BF00549096	journal	January 1977
Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces Van Regemorter, Tanguy; Guillaume, Maxime; Sini, Gjergji Theoretical Chemistry Accounts, Vol. 131, Issue 10 https://doi.org/10.1007/s00214-012-1273-0	journal	September 2012
Ab initio molecular simulations with numeric atom-centered orbitals Blum, Volker; Gehrke, Ralf; Hanke, Felix Computer Physics Communications, Vol. 180, Issue 11 https://doi.org/10.1016/j.cpc.2009.06.022	journal	November 2009
On the electron affinity of TCNQ Milián, Begoña; Pou-Amérigo, Rosendo; Viruela, Rafael Chemical Physics Letters, Vol. 391, Issue 1-3 https://doi.org/10.1016/j.cplett.2004.04.102	journal	June 2004
Organic Conductors: From Charge Density Wave TTF−TCNQ to Superconducting (TMTSF) ₂ PF ₆ Jérome, Denis Chemical Reviews, Vol. 104, Issue 11 https://doi.org/10.1021/cr030652g	journal	November 2004
Evaluating the Performance of DFT Functionals in Assessing the Interaction Energy and Ground-State Charge Transfer of Donor/Acceptor Complexes: Tetrathiafulvalene−Tetracyanoquinodimethane (TTF−TCNQ) as a Model Case Sini, Gjergji; Sears, John S.; Brédas, Jean-Luc Journal of Chemical Theory and Computation, Vol. 7, Issue 3 https://doi.org/10.1021/ct1005517	journal	January 2011
Interfacial Engineering of Organic Nanofibril Heterojunctions into Highly Photoconductive Materials Che, Yanke; Huang, Helin; Xu, Miao Journal of the American Chemical Society, Vol. 133, Issue 4 https://doi.org/10.1021/ja109396g	journal	February 2011
Understanding the Metal-Directed Growth of Single-Crystal M-TCNQF ₄ Organic Nanowires with Time-Resolved, in Situ X-ray Diffraction and First-Principles Theoretical Studies Xiao, Kai; Yoon, Mina; Rondinone, Adam J. Journal of the American Chemical Society, Vol. 134, Issue 35 https://doi.org/10.1021/ja301456p	journal	April 2012
Surface-Induced Orientation Control of CuPc Molecules for the Epitaxial Growth of Highly Ordered Organic Crystals on Graphene Xiao, Kai; Deng, Wan; Keum, Jong K. Journal of the American Chemical Society, Vol. 135, Issue 9 https://doi.org/10.1021/ja3125096	journal	February 2013
Ultrathin n-Type Organic Nanoribbons with High Photoconductivity and Application in Optoelectronic Vapor Sensing of Explosives Che, Yanke; Yang, Xiaomei; Liu, Guilin Journal of the American Chemical Society, Vol. 132, Issue 16 https://doi.org/10.1021/ja909797q	journal	March 2010
Fabrication of Field-Effect Transistors from Hexathiapentacene Single-Crystal Nanowires Briseno, Alejandro L.; Mannsfeld, Stefan C. B.; Lu, Xianmao Nano Letters, Vol. 7, Issue 3 https://doi.org/10.1021/nl0627036	journal	March 2007
Metallic conduction at organic charge-transfer interfaces Alves, Helena; Molinari, Anna S.; Xie, Hangxing Nature Materials, Vol. 7, Issue 7 https://doi.org/10.1038/nmat2205	journal	June 2008
Observation of extremely long spin relaxation times in an organic nanowire spin valve Pramanik, S.; Stefanita, C. -G.; Patibandla, S. Nature Nanotechnology, Vol. 2, Issue 4 https://doi.org/10.1038/nnano.2007.64	journal	March 2007
Long-range magnetic order in a purely organic 2D layer adsorbed on epitaxial graphene Garnica, Manuela; Stradi, Daniele; Barja, Sara Nature Physics, Vol. 9, Issue 6 https://doi.org/10.1038/nphys2610	journal	April 2013
Many-electron self-interaction error in approximate density functionals Mori-Sánchez, Paula; Cohen, Aron J.; Yang, Weitao The Journal of Chemical Physics, Vol. 125, Issue 20 https://doi.org/10.1063/1.2403848	journal	November 2006
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
Theoretical study on the charge transfer mechanism at donor/acceptor interface: Why TTF/TCNQ is inadaptable to photovoltaics? Li, Shuang-Bao; Geng, Yun; Duan, Yu-Ai The Journal of Chemical Physics, Vol. 145, Issue 24 https://doi.org/10.1063/1.4972005	journal	December 2016
What correlation effects are covered by density functional theory? He, Yuan; GrÄFenstein, JÜRgen; Kraka, Elfi Molecular Physics, Vol. 98, Issue 20 https://doi.org/10.1080/00268970009483369	journal	October 2000
Resolution-of-identity approach to Hartree–Fock, hybrid density functionals, RPA, MP2 and GW with numeric atom-centered orbital basis functions Ren, Xinguo; Rinke, Patrick; Blum, Volker New Journal of Physics, Vol. 14, Issue 5 https://doi.org/10.1088/1367-2630/14/5/053020	journal	May 2012
Exact differential equation for the density and ionization energy of a many-particle system Levy, Mel; Perdew, John P.; Sahni, Viraht Physical Review A, Vol. 30, Issue 5 https://doi.org/10.1103/PhysRevA.30.2745	journal	November 1984
Proof that ∂ E ∂ n i = ε in density-functional theory Janak, J. F. Physical Review B, Vol. 18, Issue 12 https://doi.org/10.1103/PhysRevB.18.7165	journal	December 1978
Exact results for the charge and spin densities, exchange-correlation potentials, and density-functional eigenvalues Almbladh, C. -O.; von Barth, U. Physical Review B, Vol. 31, Issue 6 https://doi.org/10.1103/PhysRevB.31.3231	journal	March 1985
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Unified description of ground and excited states of finite systems: The self-consistent G W approach Caruso, F.; Rinke, P.; Ren, X. Physical Review B, Vol. 86, Issue 8 https://doi.org/10.1103/PhysRevB.86.081102	journal	August 2012
Hybrid density functional theory meets quasiparticle calculations: A consistent electronic structure approach Atalla, Viktor; Yoon, Mina; Caruso, Fabio Physical Review B, Vol. 88, Issue 16 https://doi.org/10.1103/PhysRevB.88.165122	journal	October 2013
Formation of Dispersive Hybrid Bands at an Organic-Metal Interface Gonzalez-Lakunza, N.; Fernández-Torrente, I.; Franke, K. J. Physical Review Letters, Vol. 100, Issue 15 https://doi.org/10.1103/PhysRevLett.100.156805	journal	April 2008
Ground State of the Electron Gas by a Stochastic Method Ceperley, D. M.; Alder, B. J. Physical Review Letters, Vol. 45, Issue 7, p. 566-569 https://doi.org/10.1103/PhysRevLett.45.566	journal	August 1980
Density-Functional Theory for Fractional Particle Number: Derivative Discontinuities of the Energy Perdew, John P.; Parr, Robert G.; Levy, Mel Physical Review Letters, Vol. 49, Issue 23 https://doi.org/10.1103/PhysRevLett.49.1691	journal	December 1982
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996

Cited By (1)

Description of intermolecular charge transfer with subsystem density-functional theory Schulz, Anika; Jacob, Christoph R. The Journal of Chemical Physics, Vol. 151, Issue 13 https://doi.org/10.1063/1.5125218	journal	October 2019

Similar Records

Electronic and magnetic properties of TTF and TCNQ covered Co thin films

Journal Article · Sat May 07 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:22657968

Barrier height formation in organic blends/metal interfaces: Case of tetrathiafulvalene-tetracyanoquinodimethane/Au(111)

Journal Article · Fri Dec 06 23:00:00 EST 2013 · Journal of Chemical Physics · OSTI ID:22251296

Novel characterization of Argonne Premium coals with electron donors or acceptors by electron paramagnetic resonance spectroscopy

Conference · Thu Dec 30 23:00:00 EST 1993 · OSTI ID:441422

Related Subjects

36 MATERIALS SCIENCE
TTF-TCNQ
charge transfer
density functional theory
electron donor–acceptor molecules
hybrid functional
interface phenomena

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

Citation Formats

References (30)

Cited By (1)

Similar Records

Related Subjects