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A simplified Tamm-Dancoff density functional approach for the electronic excitation spectra of very large molecules
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10.1063/1.4811331
/content/aip/journal/jcp/138/24/10.1063/1.4811331
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/24/10.1063/1.4811331

Figures

Image of FIG. 1.
FIG. 1.

Dependence of mean absolute deviation (MAD) from reference values on the Fock exchange mixing parameter for the two test sets and for the DYE12 set also for two different selection thresholds (with = 10 being the default).

Image of FIG. 2.
FIG. 2.

Comparison of computed (PBE0/TZVP) UV-spectra for indigo at sTDA- (black) and TD(A)-DFT levels (gray).

Image of FIG. 3.
FIG. 3.

Comparison of computed (BHLYP/TZVP) UV-spectra for 9-(N-carbazolyl)-anthracene at sTDA- (black) and TD(A)-DFT levels (gray).

Image of FIG. 4.
FIG. 4.

Comparison of computed (PBE0/TZVP) charge-transfer excitation energies for the complex as a function of the intermolecular distance . The solid gray line refers to an analytical single-particle reference.

Image of FIG. 5.
FIG. 5.

Comparison of computed and experimental UV-spectra for C at the sTDA-DFT/TZVP level for two flavors of the PBE hybrid functional. Oscillator strengths for forbidden transitions have been set to = 10 in order to simulate vibronic couplings.

Image of FIG. 6.
FIG. 6.

Comparison of computed and experimental UV-spectra for [Ru(bipy)] at sTDA-PBE0/TZVP and sTDA-TPSS0/TZVP levels. The calculated spectra have been shifted by −0.23 and −0.35 eV, respectively, to obtain agreement with the experimental position of band A.

Image of FIG. 7.
FIG. 7.

Comparison of computed and experimental UV-spectra for ferrocene at the sTDA and TDA levels (PBE0/def2-TZVP). The computed spectra are not shifted. Oscillator strengths for forbidden transitions have been set to = 5 × 10 in order to simulate vibronic couplings.

Image of FIG. 8.
FIG. 8.

Comparison of computed and experimental CD-spectra for (P)-[7]helicene at the sTDA-PBE38/TZVP level for three configuration selection thresholds.

Image of FIG. 9.
FIG. 9.

(a) Comparison of computed CD-spectra for (Ala) at TD(A)-DFT and sTDA-DFT levels using the BHLYP functional and the SV(P) AO basis set. (b) Comparison of experimental and computed CD-spectra (same level as above and in addition with the TZVP basis set) for a realistic α-helix (the (Ala) structure is shown in the inset, for details see text). The intensities are normalized to the number of residues as usual and the sTDA excitation energies have been shifted by −1 eV.

Image of FIG. 10.
FIG. 10.

Comparison of computed and experimental UV-spectra for (LLL) at the sTDA-DFT level (BHLYP/TZVP for TPSS-D3(BJ)-COSMO(CHCl)/SV(P) optimized geometries). The COSMO model with a dielectric constant of 20, an energy shift of 0.3 eV, and a bandwidth of σ = 0.6 eV was applied. The theoretical intensity is scaled by a factor of 0.5 and in addition individual transitions are shown as sticks. The experimental intensity below about 230 nm is unreliable because of absorption of the solvent (1:1 mixture of CHCl/CHCN).

Tables

Generic image for table
Table I.

Comparison of calculated and experimental singlet-singlet excitation energies (in eV) for the EXC26 benchmark set. The states are ordered according to energy in two groups (more local states in entries 1–9 and delocalized ππ* states in entries 10–26).

Generic image for table
Table II.

Analysis of TDA wave functions in terms of single excitation configuration state function (CSF) coefficients for the four lowest dipole-allowed transitions of indole with sTDA and TDA (PBE0/TZVP). Given are the three largest contributions as well as the excitation energies Δ (in eV) and oscillator strengths . The letters “H” and “L” denote highest occupied and lowest unoccupied orbitals, respectively, and indicate the orbitals involved in the excitation (“from”→“to”).

Generic image for table
Table III.

Calculated (aug-cc-pVTZ, AO basis for DFT, B3LYP functional) and experimental excitation energies Δ (in eV) for vertical singlet excited states of acetone. The oscillator strengths ( ) for sTDA-DFT are given in parentheses.

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/content/aip/journal/jcp/138/24/10.1063/1.4811331
2013-06-25
2014-04-25
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A simplified Tamm-Dancoff density functional approach for the electronic excitation spectra of very large molecules
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/24/10.1063/1.4811331
10.1063/1.4811331
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