6.4 Hartree-Fock-Roothaan方程 LCAO-MO Roothann Linear Combination of Atomic Orbital-Molecular Orbital (LCAO-MO) K ，=2cnP i=1,2,K {p,}-a set of known functions:原子基or平面波基 =1 基组的选择决定了波函数的准确性 f(G)∑cmp(G)=e∑cP(G) matrix equation for the c coefficients Multiplying by()on the left and integrating we get: ∑cn∫pa()f()p,()d1=6,∑c∫pa()pv()d Fw=∫pa)fp,G)dt Fock matrix(KxK Hermitian matrix) S=()o()dr -overlap matrix(KxK Hermitian matrix) ∑Fmw=e,∑Smcu, i=1,2,,K -Roothaan equations >15 Chapter 6 HFLCAO-MO 15 Chapter 6 HF 6.4 Hartree-Fock-Roothaan方程 Roothann Linear Combination of Atomic Orbital – Molecular Orbital (LCAO-MO)  = Φ = K i i c μ 1 μϕ μ i=1,2,...,K {ϕμ} – a set of known functions : 原子基 or 平面波基 基组的选择决定了波函数的准确性