Frontier Orbital Engineering in Heteroatom-Doped Prototypical Organic Dyes for Dye-Sensitized Solar Cells

Abstract

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-$\omega$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 ($\omega_{eff}$) 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-$\pi$-acceptor (D-$\pi$-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 $\pi$-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.