skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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.

Authors:
; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Molecularly Engineered Energy Materials (MEEM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1386642
DOE Contract Number:  
SC0001342
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 137; Journal 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; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solar (photovoltaic), energy storage (including batteries and capacitors), charge transport, membrane, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Reslan, Randa, Lopata, Kenneth, Arntsen, Christopher, Govind, Niranjan, and Neuhauser, Daniel. Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer. United States: N. p., 2012. Web. doi:10.1063/1.4729047.
Reslan, Randa, Lopata, Kenneth, Arntsen, Christopher, Govind, Niranjan, & Neuhauser, Daniel. Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer. United States. doi:10.1063/1.4729047.
Reslan, Randa, Lopata, Kenneth, Arntsen, Christopher, Govind, Niranjan, and Neuhauser, Daniel. Fri . "Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer". United States. doi:10.1063/1.4729047.
@article{osti_1386642,
title = {Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer},
author = {Reslan, Randa and Lopata, Kenneth and Arntsen, Christopher and Govind, Niranjan and Neuhauser, Daniel},
abstractNote = {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.},
doi = {10.1063/1.4729047},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 22,
volume = 137,
place = {United States},
year = {2012},
month = {12}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

New coupled-cluster methods with singles, doubles, and noniterative triples for high accuracy calculations of excited electronic states
journal, January 2004

  • Kowalski, Karol; Piecuch, Piotr
  • The Journal of Chemical Physics, Vol. 120, Issue 4
  • DOI: 10.1063/1.1632474

Electron transfer with TD-Split, a linear response time-dependent method
journal, November 2011


Real-time linear response for time-dependent density-functional theory
journal, November 2004

  • Baer, Roi; Neuhauser, Daniel
  • The Journal of Chemical Physics, Vol. 121, Issue 20
  • DOI: 10.1063/1.1808412

Electron Transport in Molecular Wire Junctions
journal, May 2003


Electron transfers in chemistry and biology
journal, August 1985

  • Marcus, R. A.; Sutin, Norman
  • Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, Vol. 811, Issue 3
  • DOI: 10.1016/0304-4173(85)90014-X

Time-dependent local-density approximation in real time
journal, August 1996


Self-Consistent-Field X α Cluster Method for Polyatomic Molecules and Solids
journal, February 1972


Applications of the random phase approximation with the INDO/S Hamiltonian: UVVIS spectra of free base porphin
journal, December 1990


Modeling Fast Electron Dynamics with Real-Time Time-Dependent Density Functional Theory: Application to Small Molecules and Chromophores
journal, April 2011

  • Lopata, Kenneth; Govind, Niranjan
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 5
  • DOI: 10.1021/ct200137z

Intramolecular Long-Distance Electron Transfer in Organic Molecules
journal, April 1988


A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films
journal, October 1991

  • O'Regan, Brian; Grätzel, Michael
  • Nature, Vol. 353, Issue 6346, p. 737-740
  • DOI: 10.1038/353737a0

Charge Transport Properties in Discotic Liquid Crystals:  A Quantum-Chemical Insight into Structure−Property Relationships
journal, March 2004

  • Lemaur, Vincent; da Silva Filho, Demetrio A.; Coropceanu, Veaceslav
  • Journal of the American Chemical Society, Vol. 126, Issue 10
  • DOI: 10.1021/ja0390956

Electron tunneling in solid-state electron-transfer reactions
journal, February 1987

  • Mikkelsen, Kurt V.; Ratner, Mark A.
  • Chemical Reviews, Vol. 87, Issue 1
  • DOI: 10.1021/cr00077a007

Molecular Recognition and Conductance in Crown Ethers
journal, November 2003

  • Liu, Chris; Walter, Derek; Neuhauser, Daniel
  • Journal of the American Chemical Society, Vol. 125, Issue 46
  • DOI: 10.1021/ja029085p

Time-Dependent Theory of the Rate of Photo-induced Electron Transfer
journal, September 2011

  • Chen, Hanning; Ratner, Mark A.; Schatz, George C.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 38
  • DOI: 10.1021/jp205262u

Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
journal, August 1980

  • Vosko, S. H.; Wilk, L.; Nusair, M.
  • Canadian Journal of Physics, Vol. 58, Issue 8
  • DOI: 10.1139/p80-159

Efficient Degradation of Toxic Organic Pollutants with Ni 2 O 3 /TiO 2 - x B x under Visible Irradiation
journal, April 2004

  • Zhao, Wei; Ma, Wanhong; Chen, Chuncheng
  • Journal of the American Chemical Society, Vol. 126, Issue 15
  • DOI: 10.1021/ja0396753

Nonadiabatic Molecular Dynamics Simulation of Light-Induced Electron Transfer from an Anchored Molecular Electron Donor to a Semiconductor Acceptor
journal, August 2002

  • Stier, William; Prezhdo, Oleg V.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 33
  • DOI: 10.1021/jp014267b

Time-dependent density functional theory for radicals
journal, March 1999


octopus: a tool for the application of time-dependent density functional theory
journal, September 2006

  • Castro, Alberto; Appel, Heiko; Oliveira, Micael
  • physica status solidi (b), Vol. 243, Issue 11
  • DOI: 10.1002/pssb.200642067

Generalization of the Mulliken-Hush treatment for the calculation of electron transfer matrix elements
journal, January 1996


Extracting electron transfer coupling elements from constrained density functional theory
journal, October 2006

  • Wu, Qin; Van Voorhis, Troy
  • The Journal of Chemical Physics, Vol. 125, Issue 16
  • DOI: 10.1063/1.2360263

Reliable Prediction of Charge Transfer Excitations in Molecular Complexes Using Time-Dependent Density Functional Theory
journal, March 2009

  • Stein, Tamar; Kronik, Leeor; Baer, Roi
  • Journal of the American Chemical Society, Vol. 131, Issue 8
  • DOI: 10.1021/ja8087482

Charge-Transfer and Energy-Transfer Processes in π-Conjugated Oligomers and Polymers:  A Molecular Picture
journal, November 2004

  • Brédas, Jean-Luc; Beljonne, David; Coropceanu, Veaceslav
  • Chemical Reviews, Vol. 104, Issue 11
  • DOI: 10.1021/cr040084k

The influence of initial conditions on charge transfer dynamics
journal, January 2009

  • Eshuis, Henk; van Voorhis, Troy
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 44
  • DOI: 10.1039/b912085h

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Coupled-cluster theory in quantum chemistry
journal, February 2007


Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Electron transport in molecular junctions
journal, December 2006


A time-dependent semiempirical approach to determining excited states
journal, June 2010

  • Bartell, Lizette A.; Wall, Michael R.; Neuhauser, Daniel
  • The Journal of Chemical Physics, Vol. 132, Issue 23
  • DOI: 10.1063/1.3453683

The Electronic Couplings in Electron Transfer and Excitation Energy Transfer
journal, April 2009

  • Hsu, Chao-Ping
  • Accounts of Chemical Research, Vol. 42, Issue 4
  • DOI: 10.1021/ar800153f