●物理化学 3-1 Covalence bond Theory Covalent and lonic Binding F Contour maps of the molecular charge distributions of n, and LiF at their equilibrium internuclear separations 2021/8/21 复旦大学化学系
物理化学I 2021/8/21 复旦大学化学系 6 Contour maps of the molecular charge distributions of N2 and LiF at their equilibrium internuclear separations Covalent and Ionic Binding 3-1 Covalence bond Theory
●物理化学 3-1 Covalence bond Theory The hamiltonian of h is 十 21222M"a2M R, r=Ey(R,r) ro2 b rh2 Rab rir The underlying physical laws necessary for the mathematical theory of.. the whole of chemistry are thus completely known, and the difficulty is only that the exact application of these laws leads to equations much too complicated to be soluble. -Dirac 2021/8/21 复旦大学化学系
物理化学I 2021/8/21 复旦大学化学系 7 The Hamiltonian of H2 is (R,r) E (R,r) M M r r r r R r a a b b a b a b = − − − − − − − − + + 1 2 1 2 1 2 2 2 2 2 2 1 1 1 1 1 1 1 2 1 2 1 2 1 2 1 The underlying physical laws necessary for the mathematical theory of … the whole of chemistry are thus completely known, and the difficulty is only that the exact application of these laws leads to equations much too complicated to be soluble. ----------Dirac 3-1 Covalence bond Theory
●物理化学 3-1 Covalence bond Theory +n+v(R,r)=EV(R 2 2M 2M 12 R B.O. Approximation 2 b2 2 R Oppenheimer a b +n+u(r)=E(R)u(r) 72 2 tb 12 2021/8/21 复旦大学化学系
物理化学I 2021/8/21 复旦大学化学系 8 Rab 12 r b2 r a1 r a b 1 2 a2 r b1 r (R,r) E (R,r) M M r r r r R r a a b b a b a b = − − − − − − − − + + 1 2 1 2 1 2 2 2 2 2 2 1 1 1 1 1 1 1 2 1 2 1 2 1 2 1 (r) E(R) (r) r r r r R r a a b b a b = − − − − − − + + 1 2 1 2 1 2 2 2 2 1 1 1 1 1 1 1 2 1 2 1 B.O. Approximation Oppenheimei 3-1 Covalence bond Theory
●物理化学 3-1 Covalence bond Theory 111111 V V(r)=E(Ry(r) 2 2 a2 b2 b 12 Separate variables E HEitler and elondon's contribution 2021/8/21 复旦大学化学系
物理化学I 2021/8/21 复旦大学化学系 9 ( ) ( ) i i i i ai bi i U r r E r r r = − − − + ( ) 1 1 2 1 2 (r) E(R) (r) r r r r R r a a b b a b = − − − − − − + + 1 2 1 2 1 2 2 2 2 1 1 1 1 1 1 1 2 1 2 1 Separate Variables W.Heitler and F.London’s contribution 3-1 Covalence bond Theory
●物理化学 3-1 Covalence bond Theory 11 +n+y/(r)=E(R)(r) 2 b2 R Linear variational method Trial Eigenfunction =C1W1+C2v2 v1=v(1)(2)v2=V2(26(1 2021/8/21 复旦大学化学系
物理化学I 2021/8/21 复旦大学化学系 10 (r) E(R) (r) r r r r R r a a b b a b = − − − − − − + + 1 2 1 2 1 2 2 2 2 1 1 1 1 1 1 1 2 1 2 1 Linear Variational Method (1) (2) 1 = a b (2) (1) 2 = a b Trial Eigenfunction = C1 1 +C2 2 3-1 Covalence bond Theory