南京大学结构化学双语.pptVIP

Chapter 7 Transition-Metal Complexes Topics: 7.1 Atoms and Orbitals in Electrostatic Field Topics: Square Ligand Field p orbitals Square Ligand Field d orbitals Octahedral Ligand Field d orbitals Tetrahedral Ligand Field d orbitals 7.2 Group Theoretical Analysis Orbital Splitting in Octahedral Field Character Table Splitting of Terms Weak Field Scheme Strong Field Scheme Summary for d2 in Octahedral field, Correlation Diagram 以对称的空间波函数为例, 考察它们在O群对称操作的作用下，满足T1g 还是 T2g的基函数的要求？ 实际上，我们不必考察所用操作，只需分析 C4(z)操作即可。 因为 对于T1和T2表示的基函数，C4(z)的特征标不相等。 xy, yz, zx -1 -1 1 0 3 T2 x, y, z -1 1 -1 0 3 T1 z2, x2-y2 2 0 0 -1 2 E 1 -1 -1 1 1 A2 1 1 1 1 1 A1 3C2(C42) 6C4 6C2 8C3 I O We choose the C4 about the z-axis. Then x y z This group belong to T2g , the Spin state forT2g is 1. 1T2g + 3T1g * * Atoms and orbitals in Electrostatic Field Group Theoretical Analysis Optical Spectra and Magnetic Properties Stereochemistry Molecular Orbital Treatment ?-Bonding and Covalent Complexes Square Ligand Field Octahedral Field E0 pz px ,py E0 E0 D E0 D Topics: Orbital splitting in Octahedral Field Splitting of Terms Weak Field Scheme（弱场方案） Strong Field Scheme （强场方案） Atomic orbitals in zero field 上述基函数集合皆为中心对称力场中的不可约 表示基函数。但是，在八面体场中，可能会发 生分裂。 xy, yz, zx -1 -1 1 0 3 T2 x, y, z -1 1 -1 0 3 T1 z2, x2-y2 2 0 0 -1 2 E 1 -1 -1 1 1 A2 1 1 1 1 1 A1 3C2(C42) 6C4 6C2 8C3 I O 由群表直接可知： s = A1g p = T1u d = Eg+T2g 如何判断七个f原子轨道, 和 F,G,H 等谱项的分裂呢? Atomic orbital in general, If the rotations is about the z-axis, the only changes in the wavefunction is in 1 -1 1 -1 1 3C2(C42) A2u+T1u+T2u -1 -1 1 7 f A1g+Eg+T1g+T2g 1 1 0 9 g Eg+T2g -1 1 -1 5 d T1u 1 -1 0 3 p A1g 1 1 1 1 s Splitting Pattern 6C4 6C2 8C3 I Oh 2A1g+ A2g+ B1g+B2g+2Eg A1+E+T1+T2 A1g+Eg+T1g+T2g g A2u+B1u+B2u+2Eu A2+T1+T2 A2u+T1u+T2u f A1g+B1g+B2g+Eg E+T2 Eg+T2g d A2u+Eu T2 T1u p A1g A1 A1g s D4h Td Oh Weak field and strong field schemes Weak Field: Strong Field: Field–orbital interaction is much we