Failure of time-dependent density functional theory for long-range charge-transfer excited states: the zincbacteriochlorin-bacteriochlorin and bacteriochlorophyll-spheroidene complexes

J Am Chem Soc. 2004 Mar 31;126(12):4007-16. doi: 10.1021/ja039556n.

Abstract

It is well-known that time-dependent density functional theory (TDDFT) yields substantial errors for the excitation energies of charge-transfer (CT) excited states, when approximate standard exchange-correlation (xc) functionals are used, for example, SVWN, BLYP, or B3LYP. Also, the correct 1/R asymptotic behavior of CT states with respect to a distance coordinate R between the separated charges of the CT state is not reproduced by TDDFT employing these xc-functionals. Here, we demonstrate by analysis of the TDDFT equations that the first failure is due to the self-interaction error in the orbital energies from the ground-state DFT calculation, while the latter is a similar self-interaction error in TDDFT arising through the electron transfer in the CT state. Possible correction schemes, such as inclusion of exact Hartree-Fock or exact Kohn-Sham exchange, as well as aspects of the exact xc-functional are discussed in this context. Furthermore, a practical approach is proposed which combines the benefits of TDDFT and configuration interaction singles (CIS) and which does not suffer from electron-transfer self-interaction. The latter approach is applied to a (1,4)-phenylene-linked zincbacteriochlorin-bacteriochlorin complex and to a bacteriochlorophyll-spheroidene complex, in which CT states may play important roles in energy and electron-transfer processes. The errors of TDDFT alone for the CT states are demonstrated, and reasonable estimates for the true excitation energies of these states are given.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Bacteriochlorophylls / chemistry*
  • Carotenoids / chemistry*
  • Electron Transport
  • Energy Transfer
  • Metalloporphyrins / chemistry*
  • Models, Chemical
  • Photosynthetic Reaction Center Complex Proteins / chemistry*
  • Porphyrins / chemistry*
  • Proteobacteria / metabolism
  • Systems Theory*
  • Time Factors

Substances

  • Bacteriochlorophylls
  • Metalloporphyrins
  • Photosynthetic Reaction Center Complex Proteins
  • Porphyrins
  • bacteriochlorin
  • spheroidene
  • zinc hematoporphyrin
  • Carotenoids