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

被引:1560
作者
Dreuw, A [1 ]
Head-Gordon, M
机构
[1] Goethe Univ Frankfurt, Inst Phys & Theoret Chem, Marie Curie Str 11, D-60439 Frankfurt, Germany
[2] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[3] Univ Calif Berkeley, Lawrence Berkeley Lab, Chem Sci & Phys Biosci Div, Berkeley, CA 94720 USA
关键词
D O I
10.1021/ja039556n
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
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页码:4007 / 4016
页数:10
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