Department of Chemistry, Tokyo Metropolitan University, Hachioji, Tokyo, Japan.
Phys Chem Chem Phys. 2016 May 25;18(21):14466-78. doi: 10.1039/c6cp01461e.
We explore spin-forbidden transitions for a Ru dye with an N3 skeleton and an Fe dye with a DX1 skeleton by time-dependent density functional theory with spin-orbit interaction. The modified N3-based Ru dye with iodine anions has an absorption edge in the long wavelength region which is not observed in the original N3 dye. The long wavelength absorption edge originates from the spin-orbit interaction with iodine. Although the Fe dye has a small spin-orbit interaction, because of less spin-orbit interaction from the light metal, spin-forbidden transitions also occur for DX1-based Fe dye systems with iodine anions. This result indicates that the introduction of iodine can strengthen the spin-orbit interaction for a dye sensitizer and offers a new approach for designing spin-forbidden transitions.
我们通过含时密度泛函理论（考虑自旋轨道相互作用）探究了具有 N3 骨架的钌染料和具有 DX1 骨架的铁染料的自旋禁阻跃迁。带有碘阴离子的改良 N3 基钌染料具有原始 N3 染料中未观察到的长波长吸收边缘。长波长吸收边缘源于与碘的自旋轨道相互作用。尽管铁染料的自旋轨道相互作用较小，但由于轻金属的自旋轨道相互作用较小，带有碘阴离子的基于 DX1 的铁染料体系也会发生自旋禁阻跃迁。这一结果表明，碘的引入可以增强染料敏化剂的自旋轨道相互作用，为设计自旋禁阻跃迁提供了一种新方法。
