Zouaoui-Rabah Mourad, Elhorri Abdelkader M, Hedidi Madani, Mahdjoub-Araibi Hicham, Assia Laib, Zenati Mahammed
Laboratory of Materials Chemistry Catalysis and Reactivity, Department of Chemistry, Faculty of Exact Sciences and Informatics, Hassiba BenBouali University of Chlef, P.O. Box 78C, 02180, Oran, Ouled Fares Chlef, Algeria.
Department of Preparatory Education in Science and Technology, National Polytechnic School of Oran Maurice Audin, Box B.P, 1523, Oran, Algeria.
J Mol Model. 2025 Jun 14;31(7):191. doi: 10.1007/s00894-025-06414-8.
This computational investigation delves into the strategic design of bimetallic Zn/M organometallic D-π-A dyes for dye-sensitized solar cells (DSSCs), with a focus on how transition metals (Ti, Cr, Fe, Ni) modulate optoelectronic behavior and photovoltaic performance. Employing density functional theory (DFT) and time-dependent DFT (TD-DFT) simulations, four dyes (Dye1-Dye4) were systematically evaluated for their light-harvesting efficiency (LHE), charge transfer kinetics, and stability under vacuum and tetrahydrofuran (THF) solvation. The results underscore distinct metal-dependent trade-offs: the chromium-based dye (Dye2) demonstrates outstanding visible-light absorption (λ = 570 nm) with a high LHE (85%) and oscillator strength (f = 0.830), whereas the nickel-based dye (Dye4) exhibits redshifted absorption (λ = 609 nm) and an extended excited-state lifetime (τ = 1.55 ns), advantageous for charge separation. Titanium (Dye1) and iron (Dye3) variants emerge as economical alternatives, offering moderate efficiency and stability. THF solvation induces pronounced bathochromic shifts (+ 138 nm for Dye1) and thermodynamically favorable interactions (ΔG < - 61 kcal·mol⁻), enhancing light absorption and stability. Critical metrics such as electron injection energy (ΔG), open-circuit voltage (V), and regeneration energy (ΔG) emphasize the need to harmonize optical performance with charge management. The study advocates co-sensitization of Dye2 and Dye4 to synergistically broaden spectral response and boost power conversion efficiency. These findings pave the way for sustainable DSSCs leveraging earth-abundant metals, aligning with global initiatives for green energy innovation.
All calculations were performed with Gaussian 16. Ground state geometries were optimized by DFT with the B3LYP functional. The LanL2DZ basis set was used for transition metals, while 6-31 + + G(d,p) was used for non-metallic atoms. The solvation models studied are the CPCM (Conductor Polarizable Continuum) model and the SMD (Solvation Model Density) model. Excited state properties have been calculated using TD-DFT with the CAM-B3LYP functional to evaluate electronic transitions.
本计算研究深入探讨了用于染料敏化太阳能电池（DSSC）的双金属Zn/M有机金属D-π-A染料的战略设计，重点关注过渡金属（Ti、Cr、Fe、Ni）如何调节光电行为和光伏性能。采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）模拟，系统评估了四种染料（Dye1-Dye4）在真空和四氢呋喃（THF）溶剂化条件下的光捕获效率（LHE）、电荷转移动力学和稳定性。结果突出了不同的金属依赖性权衡：基于铬的染料（Dye2）表现出出色的可见光吸收（λ = 570 nm），具有高LHE（85%）和振子强度（f = 0.830），而基于镍的染料（Dye4）表现出红移吸收（λ = 609 nm）和延长的激发态寿命（τ = 1.55 ns），有利于电荷分离。钛（Dye1）和铁（Dye3）变体是经济的替代方案，具有适度的效率和稳定性。THF溶剂化引起明显的红移（Dye1为+138 nm）和热力学上有利的相互作用（ΔG < -61 kcal·mol⁻），增强了光吸收和稳定性。诸如电子注入能量（ΔG）、开路电压（V）和再生能量（ΔG）等关键指标强调了将光学性能与电荷管理相协调的必要性。该研究主张将Dye2和Dye4共敏化，以协同拓宽光谱响应并提高功率转换效率。这些发现为利用地球上储量丰富的金属的可持续DSSC铺平了道路，符合全球绿色能源创新倡议。
所有计算均使用Gaussian 16进行。基态几何结构通过使用B3LYP泛函的DFT进行优化。对于过渡金属使用LanL2DZ基组，对于非金属原子使用6-31++G(d,p)基组。所研究的溶剂化模型是CPCM（导体极化连续介质）模型和SMD（溶剂化模型密度）模型。使用含CAM-B3LYP泛函的TD-DFT计算激发态性质，以评估电子跃迁。
