Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 137, Issue 12, Pages -Publisher
AIP Publishing
DOI: 10.1063/1.4752431
Keywords
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Funding
- National Science Foundation (NSF) CRIF award [CHE-0946869]
- Georgia Institute of Technology
- AFOSR through the COMAS MURI program [FA9550-10-1-0558]
- AvH Foundation
- U.S. Department of Energy [DE-FG02-97ER25308]
- US National Science Foundation [CHE-1011360]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0946869] Funding Source: National Science Foundation
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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. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4752431]
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