南京大学结构化学双语课件LEC.pptVIP

BH3 : C3v BH3 CH4: Td CH4 氢原子轨道的对称性约化 {1sa, 1sb , 1sc , 1sd} SALC Transformation Matrix C2H4: D2h 5.1 Molecular Orbitals and Energy Levels 5.1 Molecular Orbitals and Energy Levels Symmetry Reduction of 12-D Basis Set MO’s of :CH2 From Fragments to the Total System 5.2 Molecular Geometry and Walsh Rule Construction of Energy-level Correlation Diagram AH2 Molecular Geometry and Walsh Rule AH3 Molecular Geometry and Walsh Rule * LCAO with the following atomic orbitals B: 2s; 2px, 2py, 2pz 3H: 1sa, 1sb, 1sc Symmetry: D3h x y a b c It is convenient to employ the sub-group D3 z x,y A1 A2 E I 2C3 3C2 D3 1 1 1 1 1 -1 2 -1 0 Character Table A1 : 2s A2 : 2pz E : 2px , 2py B原子轨道的对称性 z x,y A1 A2 E 3 0 1 ?(R) I 2C3 3C2 D3 1 1 1 1 1 -1 2 -1 0 氢原子轨道的对称性约化 {1sa, 1sb , 1sc} Construction of SALC A1: Basis function: s（亦称为全对称表示） 将所有等价原子轨道等比例加和就得到SALC x y a b c Look from upside down E: B 2s A1 subspace of molecular orbitals 2s A1 subspace 的成键图像 x y a b c px x y a b c x y a b c py x y a b c x y a b c x y a b c x y a b c x y a b c A1 subspace 的成键图像 2s 2p e(x,y) 1s(a,b,c) 2a1 3a1 1e 2e B BH3 3H a2 1a2 a1 BH3的成键图像-能级序列 2a1 1ey 2ex 1ex 4a1 1a2 ? = ? ? = x y a b c x y a b c 2ey ? x y a b c x y a b c BH3的成键图像-分子轨道图 LCAO with the following atomic orbitals C: 2s; 2px, 2py, 2pz 4H: 1sa, 1sb , 1sc , 1sd Symmetry: Td y z a b c d x a(1,1,1), b(-1,1,-1), c(1,-1,-1), d(-1,-1,1) A1 : 2s T2 : 2px , 2py (2z2-x2-y2, x2-y2) (x,y,z), (xy,yz,zx) 1 1 1 1 1 1 1 1 -1 -1 2 -1 2 0 0 3 0 -1 1 -1 3 0 -1 -1 1 A1 A2 E T1 T2 I 8C3 3C2 6S4 6sd Td The character table of group Td 碳原子： (2z2-x2-y2, x2-y2) (x,y,z), (xy,yz,zx) 1 1 1