Kurashige Yuki, Nakajima Takahito, Kurashige Saki, Hirao Kimihiko, Nishikitani Yoshinori
Department of Applied Chemistry, School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan.
J Phys Chem A. 2007 Jun 28;111(25):5544-8. doi: 10.1021/jp0720688. Epub 2007 Jun 1.
Using time-dependent density functional theory (TD-DFT), configuration interaction single (CIS) method, and approximate coupled cluster singles and doubles (CC2) method, we investigated the absorption spectra of coumarin derivative dyes (C343, NKX-2388, NKX-2311, NKX-2586, and NKX-2677), which have been synthesized for efficient dye-sensitized solar cells. The CC2 calculations are found in good agreement with the experimental results except for the smallest coumarin dye (C343). TD-DFT underestimates the vertical excitation energy of the larger coumarin dyes (NKX-2586 and -2677). Solvents (methanol) are found to induce a red shift of the vertical excitation energies, and their effects on the molecular geometry and the electronic structure are examined in detail. The deprotonated form of coumarin is also investigated, where a blue shift of the vertical excitation energies is observed.
我们使用含时密度泛函理论（TD-DFT）、单激发组态相互作用（CIS）方法以及近似耦合簇单双激发（CC2）方法，研究了为高效染料敏化太阳能电池而合成的香豆素衍生物染料（C343、NKX-2388、NKX-2311、NKX-2586和NKX-2677）的吸收光谱。除了最小的香豆素染料（C343）外，CC2计算结果与实验结果吻合良好。TD-DFT低估了较大香豆素染料（NKX-2586和-2677）的垂直激发能。发现溶剂（甲醇）会导致垂直激发能发生红移，并详细研究了它们对分子几何结构和电子结构的影响。还研究了香豆素的去质子化形式，观察到垂直激发能发生蓝移。
