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.
Skip Nav Destination
Article navigation
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
Search for other works by this author on:
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
Search for other works by this author on:
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
Search for other works by this author on:
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
Search for other works by this author on:
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
Search for other works by this author on:
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: jean-luc.bredas@chemistry.gatech.edu.
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
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Could not validate captcha. Please try again.
Sign in via your Institution
Sign in via your InstitutionPay-Per-View Access
$40.00
Citing articles via
Related Content
Does the ionization potential condition employed in QTP functionals mitigate the self-interaction error?
J. Chem. Phys. (January 2017)
Optical absorption spectra of gold clusters Aun (n = 4, 6, 8,12, 20) from long-range corrected functionals with optimal tuning
J. Chem. Phys. (September 2012)
Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory
J. Chem. Phys. (October 2014)
The performance and relationship among range-separated schemes for density functional theory
J. Chem. Phys. (August 2011)
The energy consumption optimization of the BLAS routines
AIP Conference Proceedings (July 2017)