Frontier Orbital Engineering in Heteroatom-Doped Prototypical Organic Dyes for Dye-Sensitized Solar Cells
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2026
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| author | Singh, Aditi Pandey, Ram Dhari Jana, Subrata Samal, Prasanjit Tecmer, Paweł Śmiga, Szymon |
| author_facet | Singh, Aditi Pandey, Ram Dhari Jana, Subrata Samal, Prasanjit Tecmer, Paweł Śmiga, Szymon |
| contents | The computational design of heteroatom-doped organic dyes for dye-sensitized solar cells (DSSCs) remains challenging, as predictive methods must accurately describe long-range charge-transfer (CT) excitations while remaining computationally efficient for systematic materials screening. In this work, we investigate the electronic structure and excited-state properties using the range-separated hybrid functional LC-$ω$PBE in conjunction with linear-response time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation (TDA). We employ a simplified, physically motivated, effective tuning protocol ($ω_{eff}$) to enable the rapid and reliable screening of electronic properties of organic dyes. Charge-transfer excitation energies and frontier orbital alignment the key factors governing light absorption and electron injection in DSSCs are analyzed through targeted heteroatom (N, O, and B) incorporation into donor-$π$-acceptor (D-$π$-A) organic dyes. A library of 27 mono-, di-, and tri-doped prototypical organic dyes is designed based on a carbazole donor and a cyanoacrylic acid acceptor through targeted doping at three positions of the $π$-bridge or linker. Distinct design trends emerge: electron-rich nitrogen and oxygen dopants increase the HOMO-LUMO gap and blue-shift CT excitations, with nitrogen exhibiting the strongest effect, whereas electron-deficient boron substitution narrows the gap and induces pronounced red shifts. Notably, the BBN-doped dye exhibits the smallest gap and lowest excitation energy, highlighting boron-rich motifs as promising candidates for enhanced solar light harvesting. Overall, this study establishes transferable heteroatom-doping guidelines and introduces an efficient, reliable, and cost-effective tuned DFT-TDDFT framework for high-throughput computational discovery and optimization of DSSC sensitizers. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2601_03394 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Frontier Orbital Engineering in Heteroatom-Doped Prototypical Organic Dyes for Dye-Sensitized Solar Cells Singh, Aditi Pandey, Ram Dhari Jana, Subrata Samal, Prasanjit Tecmer, Paweł Śmiga, Szymon Chemical Physics The computational design of heteroatom-doped organic dyes for dye-sensitized solar cells (DSSCs) remains challenging, as predictive methods must accurately describe long-range charge-transfer (CT) excitations while remaining computationally efficient for systematic materials screening. In this work, we investigate the electronic structure and excited-state properties using the range-separated hybrid functional LC-$ω$PBE in conjunction with linear-response time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation (TDA). We employ a simplified, physically motivated, effective tuning protocol ($ω_{eff}$) to enable the rapid and reliable screening of electronic properties of organic dyes. Charge-transfer excitation energies and frontier orbital alignment the key factors governing light absorption and electron injection in DSSCs are analyzed through targeted heteroatom (N, O, and B) incorporation into donor-$π$-acceptor (D-$π$-A) organic dyes. A library of 27 mono-, di-, and tri-doped prototypical organic dyes is designed based on a carbazole donor and a cyanoacrylic acid acceptor through targeted doping at three positions of the $π$-bridge or linker. Distinct design trends emerge: electron-rich nitrogen and oxygen dopants increase the HOMO-LUMO gap and blue-shift CT excitations, with nitrogen exhibiting the strongest effect, whereas electron-deficient boron substitution narrows the gap and induces pronounced red shifts. Notably, the BBN-doped dye exhibits the smallest gap and lowest excitation energy, highlighting boron-rich motifs as promising candidates for enhanced solar light harvesting. Overall, this study establishes transferable heteroatom-doping guidelines and introduces an efficient, reliable, and cost-effective tuned DFT-TDDFT framework for high-throughput computational discovery and optimization of DSSC sensitizers. |
| title | Frontier Orbital Engineering in Heteroatom-Doped Prototypical Organic Dyes for Dye-Sensitized Solar Cells |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2601.03394 |