Department of Physics, Periyar University, Salem 636 011, Tamilnadu, India.
Spectrochim Acta A Mol Biomol Spectrosc. 2010 Sep 15;77(1):45-50. doi: 10.1016/j.saa.2010.04.021. Epub 2010 Apr 22.
The geometries, electronic structures, polarizabilities, and hyperpolarizabilities of organic dye sensitizer 3-Phenoxyphthalonitrile were studied based on Hartree-Fock (HF) and density functional theory (DFT) using the hybrid functional B3LYP. Ultraviolet-visible (UV-vis) spectrum was investigated by time dependent DFT (TD-DFT). Features of the electronic absorption spectrum in the visible and near-UV regions were assigned based on TD-DFT calculations. The absorption bands are assigned to pi-->pi* transitions. Calculated results suggest that the three excited states with the lowest excited energies in 3-Phenoxyphthalonitrile is due to photoinduced electron transfer processes. The interfacial electron transfer between semiconductor TiO(2) electrode and dye sensitizer 3-Phenoxyphthalonitrile is due to an electron injection process from excited dye to the semiconductor's conduction band. The role of phenoxy group in 3-Phenoxyphthalonitrile in geometries, electronic structures, and spectral properties were analyzed.
基于 Hartree-Fock（HF）和密度泛函理论（DFT），使用混合函数 B3LYP 研究了有机染料敏化剂 3-苯氧基邻苯二甲腈的几何形状、电子结构、极化率和超极化率。通过时间相关密度泛函理论（TD-DFT）研究了紫外-可见（UV-vis）光谱。基于 TD-DFT 计算，对可见和近紫外区域的电子吸收光谱的特征进行了分配。吸收带归因于 pi-->pi*跃迁。计算结果表明，3-苯氧基邻苯二甲腈中具有最低激发能的三个激发态归因于光诱导电子转移过程。半导体 TiO(2)电极和染料敏化剂 3-苯氧基邻苯二甲腈之间的界面电子转移归因于从激发态染料到半导体导带的电子注入过程。分析了苯氧基在 3-苯氧基邻苯二甲腈的几何形状、电子结构和光谱性质中的作用。
