Sousa Carmen, de Graaf Coen, Rudavskyi Andrii, Broer Ria
Departament de Ciència de Materials i Química Física and Institut de Química Teòrica i Computacional, Universitat de Barcelona , C/Martí i Franquès 1, 08028 Barcelona, Catalunya, Spain.
ICREA , Pg. Lluís Companys 23, 08010 Barcelona, Catalunya, Spain.
J Phys Chem A. 2017 Dec 28;121(51):9720-9727. doi: 10.1021/acs.jpca.7b10687. Epub 2017 Dec 15.
The deactivation pathway of the light-induced spin crossover process in two Fe(II) complexes has been studied by combining density functional theory calculations for the geometries and the normal vibrational modes and highly correlated wave function methods for the energies and spin-orbit coupling effects. For the two systems considered, the mechanism of the photoinduced conversion from the low-spin singlet to the high-spin quintet state implies two intersystem crossings through intermediate triplet states. However, for the [Fe(mtz)] complex, the process occurs within few picoseconds and involves uniquely metal-centered electronic states, whereas for the [Fe(phen)] system the deactivation channel involves both metal to ligand charge transfer and metal-centered states and takes place in a femtosecond time scale.
通过结合对几何结构和正常振动模式的密度泛函理论计算以及对能量和自旋轨道耦合效应的高度相关波函数方法，研究了两种铁（II）配合物中光诱导自旋交叉过程的失活途径。对于所考虑的两个体系，从低自旋单重态到高自旋五重态的光诱导转换机制意味着通过中间三重态的两个系间窜越。然而，对于[Fe(mtz)]配合物，该过程在几皮秒内发生，且仅涉及以金属为中心的电子态，而对于[Fe(phen)]体系，失活通道涉及金属到配体的电荷转移和以金属为中心的态，并且在飞秒时间尺度内发生。
