physical chemistry8.1.pptVIP

* * ⑵ Atomic units 1a.u mass=the mass of electron m = 9.109×1028g 1a.u charge = the charge of proton e =1.602×10-19C 1a.u length =Bohr radius 1a.u energy = e2/a0 = 27.2eV 8 Molecules 8.1 Hydrogen?Molecule?Ion（H2+） The H2+ has two protons and one electron and can be described using the Schr?dinger equation ⑴The Schr?dinger equation of H2+ ⑶ The Schr?dinger equation of H2+ in a.u ①The Hamiltonian a.u ② Schr?dinger equation ⑷ The variation theorem ① The variation theorem for a linear expansion ① The estimated wave function The estimated wave function has to satisfy some conditions. Note that we have to use the correct Hamiltonian for the system, but we do not know how to solve the Schr?dinger equation for this Hamiltonian. The variation theorem tells us that: E? E The expectation value of the energy is always higher than the correct result. Molecular Orbital -- a Linear Combination of Atomic Orbitals LCAO-MO ② Expectation value of the energy〈E〉 The problem is a maximum-minimum problem in calculus. We must have: ③ The wave function ⑸ The solution of Schrodinger equation of H2+ LCAO-MO R→∞,ra→∞, ① The estimated wave function If R→∞, ra→∞, then ② The energy of H2+ All the integrals above can in principle be evaluated. We know the functions and the operator. We will just give them names: so These equations are called linear homogeneous equations. The secular determinant Haa=Hbb , Hab=Hba , Sab=Sba, and ? c1=c2 The important question is whether there is a solution other than the trivial solution. There is. The wave function disappears (the trivial solution) for all values of E except for the values of E that satisfy the determinant equation: ? c1=-c2 ③ Approximate wavefunction solve the equation for E1 Normalization solve the equation for E2 So Normalization ④ The integrals Sab, Haaand Hab （i） Sab—the overlap integral R ? 0, so Sab ? 0. If R = 0, Sab=1; R =∞, Sab= 0. （ii） Haa—Coulomb integral (