Failure of Time-Dependent Density Functional Theory for Long-Range Charge-Transfer Excited States: The Zincbacteriochlorin−Bacteriochlorin and Bacteriochlorophyll−Spheroidene Complexes Export

@article{Dreuw2004, abstract = {doi: 10.1021/ja039556n 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 HartreeFock or exact KohnSham 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 zincbacteriochlorinbacteriochlorin complex and to a bacteriochlorophyllspheroidene 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.}, author = {Dreuw, Andreas and Head-Gordon, Martin}, citeulike-article-id = {3957564}, citeulike-linkout-0 = {http://dx.doi.org/10.1021/ja039556n}, citeulike-linkout-1 = {http://pubs.acs.org/doi/abs/10.1021/ja039556n}, day = {1}, doi = {10.1021/ja039556n}, journal = {Journal of the American Chemical Society}, month = {March}, number = {12}, pages = {4007--4016}, posted-at = {2009-11-06 16:13:54}, priority = {2}, title = {Failure of Time-Dependent Density Functional Theory for Long-Range Charge-Transfer Excited States: The Zincbacteriochlorin−Bacteriochlorin and Bacteriochlorophyll−Spheroidene Complexes}, url = {http://dx.doi.org/10.1021/ja039556n}, volume = {126}, year = {2004} }

TY - JOUR ID - Dreuw2004 L3 - citeulike-article-id:3957564 N2 - doi: 10.1021/ja039556n 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 HartreeFock or exact KohnSham 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 zincbacteriochlorinbacteriochlorin complex and to a bacteriochlorophyllspheroidene 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. IS - 12 JF - Journal of the American Chemical Society EP - 4016 TI - Failure of Time-Dependent Density Functional Theory for Long-Range Charge-Transfer Excited States: The Zincbacteriochlorin−Bacteriochlorin and Bacteriochlorophyll−Spheroidene Complexes VL - 126 SP - 4007 AU - Dreuw, Andreas AU - Head-Gordon, Martin PY - 2004/03/01/ UR - http://dx.doi.org/10.1021/ja039556n ER -