Benzaldehyde dimer employed for the validation of the FDEc-TDA method. The different dimers were generated by translation of one monomer along the arrow indicated here. The figures were visualized using VMD. 96
(a) Calculated excitation energies of the benzaldehyde dimer corresponding to the lowest valence excitation energies in the monomers and (b) corresponding splitting energies calculated with the supermolecular and FDEc approach for TDDFT and TDA (BP86/TZP).
4 Å butadiene dimer structure.
Excitation energies (left) and splitting energies (right) for the (a) butadiene, (b) hexatriene, and (c) octatetraene dimer for different distances calculated with the FDE and supermolecular approach with (TDA) and without (TDDFT) the TDA (BP86/TZP).
Splitting energies for the butadiene dimer for the 1 B u excitations in the monomers calculated with the supermolecular and FDEc approach for TDDFT and TDA employing BP86/TZP and the BLYP/TZP. The reference values were obtained with CC2/TZVP.
Structural model for the astaxanthin dimer from Ref. 41 .
Structural models for the bacteriochlorophyll a (BCL)–rhodopsin glucoside (RG) pigment pairs: (a) BCL 301 (truncated) and RG 404 both from chain A and (b) BCL 305 from chain E and RG from chain C.
Calculated (BLYP/TZP) vertical optical spectra of the pigment pair rhodopsin glucoside (residue number 404) and bacteriochlorophyll a (residue number 301) with truncated phytyl chain for different theoretical models, i.e., both pigments separately (isolated), FDEu, FDEc and supermolecular calculations with (TDA) and without (TDDFT) TDA. The spectra were broadened with Gaussian line shape and a half-width of 0.05 eV. Additionally, experimental excitation energies for the individual pigments in methanol (◆, •) are shown. For 1 A g , an additional value obtained in LH2 is shown (◊). The data for the rhodopsin glucoside (RG) are taken from Ref. 92 and that for the bacteriochlorophyll a (BCL) from Ref. 89 .
Excitation energies (E) and oscillator strengths (f) for the astaxanthin dimer calculated with FDEu, FDEc, and the supermolecular approach employing the TDA and, where applicable, full TDDFT. A and B label the different monomers. However, in many cases the assignment to the excitations is ambiguous due to strong mixing with other states. The assignment was in general done according to the dominant contributions. In the supermolecular case, it was done by comparison to the FDEc calculations.
Unsigned exciton coupling constants in meV calculated for the astaxanthin dimer with FDEc different functionals with and without the TDA.
Calculated excitation energies (E) and oscillator strengths (f) for the BCL 305E–RG 402C pair from LH2 calculated with different methods, i.e., FDEu and FDEc with and without the TDA and different exchange–correlation functionals.
Absolute exciton coupling constants in meV for the BCL 305E–RG 402C pigment pair from LH2 calculated with FDEc different functionals with and without the TDA. For comparison also previously reported Coulomb couplings for similar pigment pairs in different organisms are shown.
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