A DENSITY-FUNCTIONAL STUDY OF THE MLCT STATES OF [RU(BPY)3]2+ IN D3 SYMMETRY
A DENSITY-FUNCTIONAL STUDY OF THE MLCT STATES OF [RU(BPY)3]2+ IN D3 SYMMETRY
复制标题
DOI：
10.1021/ic00094a017
复制
发表时间：
1994-08-03
影响因子：
4.6
通讯作者：
VERNOOIJS, P
中科院分区：
文献类型：
--
作者：
DAUL, C;BAERENDS, EJ;VERNOOIJS, P
采用密度泛函理论研究了[Ru（bpy）3] 2+的金属-配体电荷转移（MLCT）态.本研究中所使用的方法包括一阶静电多重态分裂以及自旋轨道相互作用。结果表明，存在一个重要的混合激发单重态和三重态。这些第一原理的结果是在良好的整体协议与所观察到的吸收光谱，相对于两个扩展的激发能量和位置的强，明确指定的峰。我们的计算发现最低激发态实际上是（dpi：a1）->（pi *：a2）3A2态的简并A1和E自旋轨道分量，前者位于后者之下几个10 cm-1单位。下一个激发三重态，即（dpi：e）-（pi *：a2）3E，仅在3A2上方约1500 cm-1处出现。
A density functional based first principles study of the metal to ligand charge-transfer (MLCT) states of [Ru(bpy)3]2+ is presented. The method used in this study includes first-order electrostatic multiplet splitting as well as spin-orbit interaction. The results obtained show that there is an important mixing of the excited singlet and triplet states. These first principles results are in good overall agreement with the observed absorption spectra, with respect to both the spread of the excitation energies and the positions of the strong, unambiguously assigned peaks. Our calculation finds the lowest excited states to be virtually degenerate A1 and E spin-orbit components of the (dpi:a1) --> (pi*:a2) 3A2 State, the former lying a few 10-cm-1 units below the latter one. The next excited triplet, i.e. (dpi:e) - (pi*:a2) 3E, arises only roughly 1500 cm-1 above the 3A2.