J Mol Model. 2025 Dec 16;32(1):18. doi: 10.1007/s00894-025-06591-6.
ABSTRACT
CONTEXT: In order to increase the efficiency of dye-sensitized solar cells (DSSC), we propose to study the influence of maximizing the push-pull effect by quantifying the donor force (Ds) and the acceptor capacity (Ap) calculated as functions of the Electrophilicity, Orbital Hardness, and Polarizability. The sum of the donor force and the acceptor capacity is the inductive force, which allows the push-pull effect to be maximized. With this approach, we applied the Barrera-Crivelli-Loeb (BCL) model to a series of eleven Zinc Porphyrins to correlate the Global Efficiency Index (GEI) with the experimental measurement of Photo Conversion Efficiency (PCE). The use of this strategy together with the use of siloles and siloxanes allows the design of two new dyes, BCL 516 and BCL 520, with theoretically calculated efficiencies of 10.64% and 10.61%.
METHODS: In this work, all calculations were performed with the Amsterdam Density Functional 2023 package. For geometry optimization (ground state and first singlet), the optimized Perdew-Becke-Ernzerhof exchange correlation functional was employed with a DZP basis set for H, C, N, O, S, and a Zeroth Order Regular Approximation (ZORA) – TZP basis set for Ti and Zn. Time-Dependent Density Functional Theory (TDDFT) calculations were achieved with the Statistical Average Orbital model exchange correlation potential (SAOP), including solvent effects with the Conductor-like Screening Model (COSMO). Calculations of molecular properties like electrophilicity, orbital hardness, and polarizability were carried out in the gas phase with the SAOP potential model after optimization of the target molecule with the OPBE exchange correlation functional. To determine the orbital hardness of the HOMO and LUMO, the occupation number of the frontier orbital was modified by 0.3 units.
PMID:41400849 | DOI:10.1007/s00894-025-06591-6
