Great attention is being shifted to Dye-sensitized solar cells because of their structural and electronic tunability, high performance, and low cost compared to conservative photovoltaic devices. In this work, the DFT/B3LYP/6-31G(d,p) and TD-DFT/mPW9PW91/6-31G(d,p) levels of theory are applied to the theoretical study of a new class of benzocarbazole-based D-A´-π-A dyes for their potential use in DSSCs. The influence of the internal acceptor on the optoelectronic properties is studied for the dyes. The optoelectronic and photovoltaic properties as HOMO, LUMO, E_{gap} maximum absorption wavelength (λ_{max}), vertical excitation energies (E_{ex}), oscillator strength (f), light harvesting efficiency (LHE), open circuit voltage (V_{oc}), injection force (ΔG_{inject)}, were evaluated and discussed in order to compare their performance as DSSC sensitizers. The theoretical results show that all dyes exhibit excellent optoelectronic properties, such as a lower E_{gap}(1.733 eV to 2.173 eV), a significant λ_{max}(631.48 nm to 754.40 nm), a sufficient value of V_{oc} (0.461 V to 0.880 V) and high LHE (0.853 eV to 0.968 eV). In particular M4 with 2,5-dihydropyrrolo [3,4-c]pyrrole-1,4-dithione as auxiliary acceptor has the potential to be used as a sensitizer for DSSCs, due to its red-shifted absorption spectrum (λ_{max}= 754.40 nm), and small energy gap (E_{gap}=1.733 eV). Indeed, this study may help chemists to synthesize efficient dyes for DSSC.
Published in | International Journal of Computational and Theoretical Chemistry (Volume 12, Issue 1) |
DOI | 10.11648/j.ijctc.20241201.11 |
Page(s) | 1-9 |
Creative Commons |
This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited. |
Copyright |
Copyright © The Author(s), 2024. Published by Science Publishing Group |
Benzocarabzole, DFT/TD-DFT, Auxiliary Acceptor, Photovoltaic Properties, Dye-sensitized Solar Cells
3.1. Optimized Ground-state Geometries
Dye | ɸ_{1} | ɸ_{2} | ɸ_{3} | d_{1} | d_{2} | d_{3} |
---|---|---|---|---|---|---|
R | -50.25 | 1.61 | 0.01 | 1.481 | 1.456 | 1.426 |
M1 | 50.28 | -1.76 | 0.03 | 1.481 | 1.455 | 1.429 |
M2 | 41.08 | -0.52 | -0.23 | 1.464 | 1.432 | 1.425 |
M3 | -20.83 | -2.20 | 0.48 | 1.449 | 1.430 | 1.429 |
M4 | -31.06 | -4.89 | 0.25 | 1.448 | 1.432 | 1.431 |
3.2. Electronic Properties and Frontier Molecular Orbitals (FMOs)
Dye | ${\mathbf{E}}_{\mathbf{HOMO}}\mathbf{\left(}\mathbf{eV}\mathbf{\right)}$ | ${\mathbf{E}}_{\mathbf{LUMO}}\mathbf{\left(}\mathbf{eV}\mathbf{\right)}$ | ${\mathbf{E}}_{\mathbf{gap}}\mathbf{\left(}\mathbf{eV}\mathbf{\right)}$ |
---|---|---|---|
R | -5.327 | -3.120 | 2.207 (2.13)^{[a]} |
M1 | -5.326 | -3.189 | 2.137 |
M2 | -5.230 | -3.152 | 2.077 |
M3 | -5.186 | -3.273 | 1.913 |
M4 | -5.272 | -3.539 | 1.733 |
TiO_{2} | - | -4.000 | - |
3.3. Photovoltaic Properties
Dye | ${\mathbf{E}}^{\mathbf{dye}}$ | ${\mathbf{E}}^{\mathbf{dye}\mathbf{*}}$ | ${\mathbf{\Delta G}}_{\mathbf{inject}}$ | LHE | ${\mathbf{V}}_{\mathbf{oc}}$ |
---|---|---|---|---|---|
R | 5.327 | 3.355 | -0.645 | 0.737 | 0.880 |
M1 | 5.326 | 3.363 | -0.637 | 0.853 | 0.811 |
M2 | 5.230 | 3.388 | -0.612 | 0.925 | 0.848 |
M3 | 5.186 | 3.415 | -0.585 | 0.968 | 0.727 |
M4 | 5.272 | 3.628 | -0.371 | 0.888 | 0.461 |
3.4. Optical Properties
Functional | ${\mathbf{\lambda}}_{\mathbf{max}}$a/(nm) | εa /(M-1.cm-1) |
---|---|---|
B3LYP | 455, 676 | 30466, 21228 |
BHandLYP | 386, 498 | 21963, 41746 |
CAM-B3LYP | 381, 484 | 19263, 44112 |
PBE0 | 502, 921 | 22378, 15295 |
mPW1PW91 | 437, 628 | 31248, 23900 |
Experimental* | 405, 489 | 33269, 20545 |
Dye | ${\mathbf{\lambda}}_{\mathbf{max}}\mathbf{\left(}\mathbf{nm}\mathbf{\right)}$ | ${\mathbf{E}}_{\mathbf{ex}}\mathbf{\left(}\mathbf{eV}\mathbf{\right)}$ | f | Main composition |
---|---|---|---|---|
R | 628.58 | 1.972 | 0.582 | H → L (0.69) |
437.66 | 2.833 | 0.735 | H-2 → L (0.69) | |
M1 | 631.48 | 1.963 | 0.835 | H → L (0.69) |
471.73 | 2.628 | 0.904 | H-1 → L (0.63) | |
M2 | 673.11 | 1.842 | 1.128 | H → L (0.70) |
482.58 | 2.569 | 0.661 | H-1 → L (0.52) | |
M3 | 699.75 | 1.772 | 1.498 | H → L (0.70) |
410.08 | 3.023 | 0.489 | H-3 → L (0.66) | |
M4 | 754.40 | 1.644 | 0.953 | H → L (0.70) |
503.92 | 2.460 | 0.136 | H → L+1 (0.53) |
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APA Style
Etabti, H., Fitri, A., Benjelloun, A. T., Benzakour, M., Mcharfi, M. (2024). A DFT/TD-DFT Study of the Influence of Anchoring Group and Internal Acceptor of Benzocarbazole-based D-A´-π-A Dyes for DSSCs. International Journal of Computational and Theoretical Chemistry, 12(1), 1-9. https://doi.org/10.11648/j.ijctc.20241201.11
ACS Style
Etabti, H.; Fitri, A.; Benjelloun, A. T.; Benzakour, M.; Mcharfi, M. A DFT/TD-DFT Study of the Influence of Anchoring Group and Internal Acceptor of Benzocarbazole-based D-A´-π-A Dyes for DSSCs. Int. J. Comput. Theor. Chem. 2024, 12(1), 1-9. doi: 10.11648/j.ijctc.20241201.11
AMA Style
Etabti H, Fitri A, Benjelloun AT, Benzakour M, Mcharfi M. A DFT/TD-DFT Study of the Influence of Anchoring Group and Internal Acceptor of Benzocarbazole-based D-A´-π-A Dyes for DSSCs. Int J Comput Theor Chem. 2024;12(1):1-9. doi: 10.11648/j.ijctc.20241201.11
@article{10.11648/j.ijctc.20241201.11, author = {Hanane Etabti and Asmae Fitri and Adil Touimi Benjelloun and Mohammed Benzakour and Mohammed Mcharfi}, title = {A DFT/TD-DFT Study of the Influence of Anchoring Group and Internal Acceptor of Benzocarbazole-based D-A´-π-A Dyes for DSSCs }, journal = {International Journal of Computational and Theoretical Chemistry}, volume = {12}, number = {1}, pages = {1-9}, doi = {10.11648/j.ijctc.20241201.11}, url = {https://doi.org/10.11648/j.ijctc.20241201.11}, eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ijctc.20241201.11}, abstract = {Great attention is being shifted to Dye-sensitized solar cells because of their structural and electronic tunability, high performance, and low cost compared to conservative photovoltaic devices. In this work, the DFT/B3LYP/6-31G(d,p) and TD-DFT/mPW9PW91/6-31G(d,p) levels of theory are applied to the theoretical study of a new class of benzocarbazole-based D-A´-π-A dyes for their potential use in DSSCs. The influence of the internal acceptor on the optoelectronic properties is studied for the dyes. The optoelectronic and photovoltaic properties as HOMO, LUMO, Egap maximum absorption wavelength (λmax), vertical excitation energies (Eex), oscillator strength (f), light harvesting efficiency (LHE), open circuit voltage (Voc), injection force (ΔGinject), were evaluated and discussed in order to compare their performance as DSSC sensitizers. The theoretical results show that all dyes exhibit excellent optoelectronic properties, such as a lower Egap(1.733 eV to 2.173 eV), a significant λmax(631.48 nm to 754.40 nm), a sufficient value of Voc (0.461 V to 0.880 V) and high LHE (0.853 eV to 0.968 eV). In particular M4 with 2,5-dihydropyrrolo [3,4-c]pyrrole-1,4-dithione as auxiliary acceptor has the potential to be used as a sensitizer for DSSCs, due to its red-shifted absorption spectrum (λmax= 754.40 nm), and small energy gap (Egap=1.733 eV). Indeed, this study may help chemists to synthesize efficient dyes for DSSC. }, year = {2024} }
TY - JOUR T1 - A DFT/TD-DFT Study of the Influence of Anchoring Group and Internal Acceptor of Benzocarbazole-based D-A´-π-A Dyes for DSSCs AU - Hanane Etabti AU - Asmae Fitri AU - Adil Touimi Benjelloun AU - Mohammed Benzakour AU - Mohammed Mcharfi Y1 - 2024/04/29 PY - 2024 N1 - https://doi.org/10.11648/j.ijctc.20241201.11 DO - 10.11648/j.ijctc.20241201.11 T2 - International Journal of Computational and Theoretical Chemistry JF - International Journal of Computational and Theoretical Chemistry JO - International Journal of Computational and Theoretical Chemistry SP - 1 EP - 9 PB - Science Publishing Group SN - 2376-7308 UR - https://doi.org/10.11648/j.ijctc.20241201.11 AB - Great attention is being shifted to Dye-sensitized solar cells because of their structural and electronic tunability, high performance, and low cost compared to conservative photovoltaic devices. In this work, the DFT/B3LYP/6-31G(d,p) and TD-DFT/mPW9PW91/6-31G(d,p) levels of theory are applied to the theoretical study of a new class of benzocarbazole-based D-A´-π-A dyes for their potential use in DSSCs. The influence of the internal acceptor on the optoelectronic properties is studied for the dyes. The optoelectronic and photovoltaic properties as HOMO, LUMO, Egap maximum absorption wavelength (λmax), vertical excitation energies (Eex), oscillator strength (f), light harvesting efficiency (LHE), open circuit voltage (Voc), injection force (ΔGinject), were evaluated and discussed in order to compare their performance as DSSC sensitizers. The theoretical results show that all dyes exhibit excellent optoelectronic properties, such as a lower Egap(1.733 eV to 2.173 eV), a significant λmax(631.48 nm to 754.40 nm), a sufficient value of Voc (0.461 V to 0.880 V) and high LHE (0.853 eV to 0.968 eV). In particular M4 with 2,5-dihydropyrrolo [3,4-c]pyrrole-1,4-dithione as auxiliary acceptor has the potential to be used as a sensitizer for DSSCs, due to its red-shifted absorption spectrum (λmax= 754.40 nm), and small energy gap (Egap=1.733 eV). Indeed, this study may help chemists to synthesize efficient dyes for DSSC. VL - 12 IS - 1 ER -