The ability of Time-Dependent Density Functional Theory (TD-DFT) to provide excited state geometries and reproduce emission energies of organic D-π-A dyes designed for DSSC applications is evaluated. The performance of six functionals (CAM-B3LYP, MPW1K, ωB97X-D, LC-BLYP, LC-ωPBE, and M06-HF) in combination with three basis sets (cc-pVDZ, 6-31+G(d,p), and 6-311+G(2d,p)) has been analyzed. Solvent effects have been taken into account by means of a Polarizable Continuum Model in both LR and SS formalisms. Our LR-PCM/TD-DFT results show that accurate emission energies are obtained only when solvent effects are included in the computation of excited state geometries and when a range separated hybrid functional is used. Vertical emission energies are reproduced with a mean absolute error of at most 0.2 eV. The accuracy is further improved using the SS-PCM formalism. © 2014 American Chemical Society.
Bernini, C., Zani, L., Calamante, M., Reginato, G., Mordini, A., Taddei, M., et al. (2014). Excited state geometries and vertical emission energies of solvated dyes for DSSC: a PCM/TD-DFT benchmark study. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 10(9), 3925-3933 [10.1021/ct500328t].
Excited state geometries and vertical emission energies of solvated dyes for DSSC: a PCM/TD-DFT benchmark study
BERNINI, CATERINA;TADDEI, MAURIZIO;BASOSI, RICCARDO;SINICROPI, ADALGISA
2014-01-01
Abstract
The ability of Time-Dependent Density Functional Theory (TD-DFT) to provide excited state geometries and reproduce emission energies of organic D-π-A dyes designed for DSSC applications is evaluated. The performance of six functionals (CAM-B3LYP, MPW1K, ωB97X-D, LC-BLYP, LC-ωPBE, and M06-HF) in combination with three basis sets (cc-pVDZ, 6-31+G(d,p), and 6-311+G(2d,p)) has been analyzed. Solvent effects have been taken into account by means of a Polarizable Continuum Model in both LR and SS formalisms. Our LR-PCM/TD-DFT results show that accurate emission energies are obtained only when solvent effects are included in the computation of excited state geometries and when a range separated hybrid functional is used. Vertical emission energies are reproduced with a mean absolute error of at most 0.2 eV. The accuracy is further improved using the SS-PCM formalism. © 2014 American Chemical Society.File | Dimensione | Formato | |
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https://hdl.handle.net/11365/47671
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