In this report, DFT and TDDFT calculations used to explain the noticeable difference in the power conversion efficiencies (PCEs) of three reported triphenylamine-based organic dyes with mono-, di-, and tri-cyanoacrylic acid units as anchoring groups, and thiophene unit as π-bridges used as potential dyes in dye-sensitized solar cell applications. These dyes were showed the superiority of the multi-anchoring systems over the mono-anchoring system. The light was shed on the effect of various functionals, e.g., B3LYP, CAM-B3LYP,$\text{ωB}97\text{XD}$, M06, PBE0 and BHandHLYP on absorption spectra. The CAM-B3LYP functional was depicted the best among numerous adopted functionals which reproduced the experimental absorption data. The geometries, electronic structures and UV-Vis absorption spectra of the isolated dyes and their adsorbed [email protected]₂ complexes were calculated. The associated physical parameters that control the effectiveness of the cell, such as the light harvesting efficiency ($LHE$), hole and electron reorganization energies (${\lambda }_{hole}$, and ${\lambda }_{ele}$), and the driving force for electron injection ($\Delta G_{inj}$) and dye regeneration ($\Delta G_{reg}$) were computed and analyzed in order to determine their contributions to the open-circuit photovoltage ($V_{oc}$) or the short-circuit photocurrent density ($J_{sc}$), and correlate the structure with property. Also, charge transfer descriptors, such as the charge transfer distance ($D^{CT}$), the amount of charge transferred ($q^{CT}$), and dipole moment (${\mu }^{CT}$) were investigated. The results reveal that the increasing of anchoring groups made significant influence on the PCE of the cells. The effect of mono-, di-, and tri-substituted anchored cyanoacrylic acid group(s) on the triphenylamine-TiO₂ complexes has been explored on the frontier molecular orbitals, binding energies and absorption wavelengths. Among all the studied derivatives, electron injection energy barrier for TPA3T3A has been found the smallest which revealed that electron injection in this compound might be superior to other counterparts. Low-lying lowest unoccupied molecular orbital of TPA3T3A would favor it to stabilize thermodynamically. Moreover, [email protected]₂ cluster was observed the most stable adsorption complex especially anchoring of TPA3T3A sensitizer at TiO₂ cluster from B-side. Comprehensible intramolecular charge transfer has been observed from occupied to unoccupied molecular orbitals. The red shift in the absorption spectra has been perceived by increasing the number of anchoring groups, i.e., cyanoacrylic acid. The type-II band gap alignment between triphenylamine-based organic sensitizers and TiO₂ is revealing that photovoltaic efficiency in these studied derivatives would be enhanced. Our quantum chemical analysis explored that these TPA derivatives especially tri-anchored dye would be proficient to be used in photovoltaic devices which would enhance the solar cell efficiency.

在本报告中，DFT和TDDFT计算用于解释三种报道的三苯基胺基有机染料的功率转换效率（PCE）的显着差异，其中单，二和三氰基丙烯酸单元作为锚定基团，噻吩单元作为π桥，在染料敏化太阳能电池应用中用作潜在的染料。这些染料显示出多锚固系统优于单锚固系统。借助各种功能（例如B3LYP，CAM-B3LYP，$\text{ωB}97\text{XD}$，M06，PBE0和BHandHLYP的吸收光谱。CAM-B3LYP的功能被描绘为众多采用的功能中最好的，它们再现了实验吸收数据。计算了分离出的染料及其吸附的[受电子邮件保护的] ₂配合物的几何形状，电子结构和UV-Vis吸收光谱。控制细胞效力的相关物理参数，例如光收集效率（$\mathrm{大号}HE$），空穴和电子重组能（${\lambda }_{HØ升Ë}$， 和 ${\lambda }_{Ë升Ë}$），以及电子注入的驱动力（$\Delta G_{\mathrm{一世}ñĴ}$）和染料再生（$\Delta G_{\mathrm{[R}ËG}$计算并分析），以确定它们对开路光电压（${\mathrm{伏特}}_{ØC}$）或短路光电流密度（${Ĵ}_{sC}$），并将结构与属性相关联。另外，电荷转移描述符，例如电荷转移距离（$d^{CŤ}$），转帐的金额（$q^{CŤ}$）和偶极矩（${\mu }^{CŤ}$）进行了调查。结果表明，锚定基团的增加对细胞的PCE产生了显着影响。在前沿分子轨道，结合能和吸收波长上，研究了单，双和三取代的锚固氰基丙烯酸基团对三苯胺-TiO ₂配合物的影响。在所有研究的衍生物中，TPA3T3A的电子注入能垒最小，这表明该化合物中的电子注入可能优于其他化合物。TPA3T3A的最低空位最低未占据分子轨道将有助于其热力学稳定。此外，观察到[电子邮件保护] ₂簇是最稳定的吸附复合物，尤其是TPA3T3A敏化剂在TiO2上的锚固从B侧开始_2个群集。已经观察到从占据到未占据的分子轨道的可理解的分子内电荷转移。通过增加锚定基团，即氰基丙烯酸的数目，可以看出吸收光谱中的红移。三苯胺基有机敏化剂和TiO ₂之间的II型带隙排列表明，这些研究的衍生物的光伏效率将得到提高。我们的量子化学分析表明，这些TPA衍生物，特别是三锚固染料，将能够熟练用于光伏装置中，从而提高太阳能电池的效率。