Facultad de Ingeniería Mochis, Universidad Autónoma de Sinaloa, Prol. Ángel Flores y Fuente de Poseidón, S/N, Los Mochis 81223, Sinaloa, Mexico.
Laboratorio Virtual NANOCOSMOS, Departamento de Medio Ambiente y Energía, Centro de Investigación en Materiales Avanzados, Miguel de Cervantes 120, Complejo Industrial Chihuahua, Chihuahua 31136, Chihuahua, Mexico.
Molecules. 2020 Aug 12;25(16):3670. doi: 10.3390/molecules25163670.
Eight novel metal-free organic sensitizers were proposed for dye-sensitized solar cells (DSSCs), theoretically calculated and studied via density functional theory with D-π-A structure. These proposals were formed to study the effect of novel π-bridges, using carbazole as the donor group and cyanoacrylic acid as the anchorage group. Through the M06/6-31G(d) level of theory, ground state geometry optimization, vibrational frequencies, the highest occupied molecular orbital, the lowest unoccupied molecular orbital, and their energy levels were calculated. Further, chemical reactivity parameters were obtained and analyzed, such as chemical hardness (η), electrophilicity index (ω), electroaccepting power (ω+) and electrodonating power (ω-). Free energy of electron injection (ΔGinj) and light-harvesting efficiency (LHE) also were calculated and discussed. On the other hand, absorption wavelengths, oscillator strengths, and electron transitions were calculated through time-dependent density functional theory with the M06-2X/6-31G(d) level of theory. In conclusion, the inclusion of thiophene groups and the Si heteroatom in the π-bridge improved charge transfer, chemical stability, and other optoelectronic properties of carbazole-based dyes.
提出了 8 种新型无金属有机敏化剂用于染料敏化太阳能电池（DSSC），通过具有 D-π-A 结构的密度泛函理论进行了理论计算和研究。这些方案的提出是为了研究新型π桥的影响，使用咔唑作为供体基团和氰基丙烯酸作为锚固基团。通过 M06/6-31G(d)理论水平，计算并优化了基态几何形状、振动频率、最高占据分子轨道（HOMO）、最低未占据分子轨道（LUMO）及其能级。此外，还获得并分析了化学反应性参数，如化学硬度（η）、电导率指数（ω）、电接受能力（ω+）和电供体能力（ω-）。还计算和讨论了电子注入自由能（ΔGinj）和光捕获效率（LHE）。另一方面，通过含时密度泛函理论（TD-DFT）与 M06-2X/6-31G(d)理论水平，计算了吸收波长、振子强度和电子跃迁。总之，在π桥中引入噻吩基团和 Si 杂原子提高了咔唑基染料的电荷转移、化学稳定性和其他光电性能。
