(日本东北大学固体物理学教材)Molecular orbital (MO) method.pptVIP

Solid state physics (SAITO) ６. Molecular orbital (MO) method(1) Tight-binding (LCAO) method numerical calculation of matrix elements 2002/10/12 Solid state physics (SAITO) Tight-binding method of molecules Approximate molecule orbitals by atomic orbitals Energy cf. Bloch orbital of solids Neglect electron-electron interaction, include to one electron interaction ? quadratic term of c (one electron approximation) Variation condition Secular equation TB of Boron(B) (regular triangle) Atomic wave function at (Hamiltonian matrix) (Overlap matrix) and are complex numbers 　integrate independently Solid state physics (SAITO) Secular equation Variation condition → N equations Secular equation Not solve the determinant ?diagonalize of the matrix Variation condition Overlap matrix Hamiltonian matrix Solid state physics (SAITO) Step of calculation Substitute H, S matrices Diagonalization library of matrices Eigenvalue 　　, eigenvector Occupy electrons from lower energy example： Hydrogen molecule Ｈ2 1s two orbitals, two electrons K-th eigenfunction Mulliken’s charge Sum by occupied orbital k ?Calculate eigenvalue and eigenfunction Charge of hte i-th atom Solid state physics (SAITO) Result of hydrogen molecule H2　 Energy Wave function Ｈ Ｈ２ Simplest approximation gain of 2t energy by bonding Covalent bonding normalization Similarly Molecular orbital of oxygen Solid state physics (SAITO) Slater-Koster’s method In the case of different atomic orbital axis p-orbital is possible to rotate as same as vector ? decompose into components of direction In the case of placing 3-dimension skew ?Rotate after projecting to 2-dimension Solid state physics (SAITO) C2 cluster C2 cluster 2s,2p(x,y,z)　4 orbitals, 2 atoms Total 8 orbitals, 8 electrons Diagonal component　 A B ８ｘ８ matrix Solid state physics (SAITO) Numerical calculation Substitute parameters and diagonalize numerically (not use det=0) Calculate eigenvalue and eigenfunction Real system, parameter