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使用DFT和TD-DFT方法研究配合物[PcRu(RPy)(Py-COOH)](Pc为酞菁;Py为吡啶;R分别代表COOH,CN,H,Me和OMe)以及它们的单、双电子氧化衍生物的电子结构和吸收光谱,分析表明中性配合物分子要比其氧化态更适合做染料.计算配合物在350 nm处有一个较强的Soret高能吸收带,而在600 nm的Q带吸收相对较弱.这些电子光谱被指认为酞菁环内的π→π*跃迁和Ru→Py-COOH电荷转移.由于染料是通过轴向吡啶上的羧酸与半导体光阳极相联接,所以配合物的π→π*跃迁对随后的电子注入没有贡献;加之该类配合物在400~580 nm可见光区无吸收,解释了该类配合物染料敏化太阳能电池光电转换效率低的原因.
The complex [PcRu (RPy) (Py-COOH)] (Pc is phthalocyanine; Py is pyridine; R stands for COOH, CN, H, Me and OMe, respectively) and their mono- and bis The electronic structure and absorption spectra of the electronic oxidation derivatives show that the neutral complexes are more suitable than their oxidation states for the dyestuffs.The calculated complexes have a strong Soret absorption band at 350 nm, Q band absorption is relatively weak.These electronic spectra are designated as π → π * transitions within the phthalocyanine ring and Ru → Py-COOH charge transfer.As the dye is coupled to the semiconductor photoanode by the carboxylic acid on the axial pyridine, Therefore, the π → π * transition of the complex does not contribute to the subsequent electron injection. Moreover, this kind of complex does not absorb in the visible region of 400-580 nm, which explains the reason of the low photoelectric conversion efficiency of the dye-sensitized solar cells.