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Excitation energies and Stokes shifts from a restricted open-shell Kohn-Sham approach
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Image of FIG. 1.
FIG. 1.

Relaxation of Kohn-Sham orbitals (a) in ΔSCF, and (b) in ROKS. Note that the converged mixed and triplet determinants in ΔSCF are constructed from different KS orbitals, whereas in ROKS both determinants are built from a common set of orbitals. Furthermore, the α and β orbital sets are identical in ROKS.

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FIG. 2.

Collection of organic dyes for the assessment of DFT Stokes shifts.


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Table I.

Lowest ROKS vertical excitation energy (in eV) for a collection of small organic dyes, compared with ab initio best-estimates.

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Table II.

Mean error (ME), mean absolute error (MAE), and root-mean-square deviation (RMSD) of ROKS excitation energies from experiment for the test set of larger organic dyes (in eV). The 6-31G* basis set was used for each constituent calculation. Functionals are arranged in order of increasing degree of exact exchange.

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Table III.

Aborption/emission energies and Stokes shift (S.S.) of each dye in Figure 2 , calculated by TDDFT, ΔSCF, and ROKS, versus experiment. All energies are in eV, and all calculations use the B3LYP functional and 6-31G* basis set. Statistics at the bottom of the table are ME, MAE, and RMSD of each method versus experiment, all in eV.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Excitation energies and Stokes shifts from a restricted open-shell Kohn-Sham approach