Predicting accurate bond-length alternations (BLAs) in long conjugated molecular chains has been a major challenge for electronic-structure theory for many decades. While Hartree-Fock (HF) overestimates BLA significantly, second-order perturbation theory and commonly used density functional theory (DFT) approaches typically underestimate it. Here, we discuss how this failure is related to the many-electron self-interaction error (MSIE), which is inherent to both HF and DFT approaches. We use tuned long-range corrected hybrids to minimize the MSIE for a series of polyenes. The key result is that the minimization of the MSIE alone does not yield accurate BLAs. On the other hand, if the range-separation parameter is tuned to yield accurate BLAs, we obtain a significant MSIE that grows with chain length. Our findings demonstrate that reducing the MSIE is one but not the only important aspect necessary to obtain accurate BLAs from density functional theory.
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28 September 2012
Research Article|
September 24 2012
On the relationship between bond-length alternation and many-electron self-interaction error
Thomas Körzdörfer;
Thomas Körzdörfer
a)
School of Chemistry and Biochemistry, Center for Organic Photonics and Electronics, and Center for Computational Molecular Science and Technology,
Georgia Institute of Technology
, Atlanta, Georgia 30332-0400, USA
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Robert M. Parrish;
Robert M. Parrish
School of Chemistry and Biochemistry, Center for Organic Photonics and Electronics, and Center for Computational Molecular Science and Technology,
Georgia Institute of Technology
, Atlanta, Georgia 30332-0400, USA
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John S. Sears;
John S. Sears
School of Chemistry and Biochemistry, Center for Organic Photonics and Electronics, and Center for Computational Molecular Science and Technology,
Georgia Institute of Technology
, Atlanta, Georgia 30332-0400, USA
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C. David Sherrill;
C. David Sherrill
School of Chemistry and Biochemistry, Center for Organic Photonics and Electronics, and Center for Computational Molecular Science and Technology,
Georgia Institute of Technology
, Atlanta, Georgia 30332-0400, USA
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Jean-Luc Brédas
Jean-Luc Brédas
b)
School of Chemistry and Biochemistry, Center for Organic Photonics and Electronics, and Center for Computational Molecular Science and Technology,
Georgia Institute of Technology
, Atlanta, Georgia 30332-0400, USA
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Thomas Körzdörfer
a)
Robert M. Parrish
John S. Sears
C. David Sherrill
Jean-Luc Brédas
b)
School of Chemistry and Biochemistry, Center for Organic Photonics and Electronics, and Center for Computational Molecular Science and Technology,
Georgia Institute of Technology
, Atlanta, Georgia 30332-0400, USA
a)
Permanent address: Computational Chemistry, University of Potsdam, D-14476 Potsdam, Germany.
b)
Also at Department of Chemistry, King Abdulaziz University, Jeddah 21589, Saudi Arabia. E-mail: [email protected].
J. Chem. Phys. 137, 124305 (2012)
Article history
Received:
July 02 2012
Accepted:
August 30 2012
Citation
Thomas Körzdörfer, Robert M. Parrish, John S. Sears, C. David Sherrill, Jean-Luc Brédas; On the relationship between bond-length alternation and many-electron self-interaction error. J. Chem. Phys. 28 September 2012; 137 (12): 124305. https://doi.org/10.1063/1.4752431
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