Chapter 2PPT.ppt

Chapter 2 1. Solution for H-like atom/ion (one-electron system) radial angular functions of Atomic orbitals, electron cloud, quantum numbers (n, l, m, and ms) electronic orbital/spin angular momentum space quantization. Atomic-orbital wavefunctions are eigenfunctions of such operators as H, L2, Lz! Summary Magnitude of orbital angular momentum Note: Angular momentum L is a vector! Key points: For H-like atom/ions, the wavefunctions to describe their atomic orbitals (AO?s) that are derived from their their Schrodinger equations can be characterized using three quantum numbers, i.e., n, l, m, and symbolized as ?nlm. They are eigenfunctions of those hermitian operators ?, L2 (M2) and Lz (Mz), by the following eigenequations, ^ ^ ^ ^ Chapter 2 Solution for many-electron atom a) Separation of variables ---- Independent particle approximation (mean field model) ? i) one-particle eigenequations ii) wavefunction of all electrons = product of one-particle eigenfunctions. iii) one-particle eigenfunctions ? atomic orbitals of H-like atoms. attainable by HF-SCF process. b) Slater’s approximation: screen constant effective nuclear charge. Summary c) Addition of Angular momenta and its physical meaning/applications in understanding electronic states of many-e atom. i) Details of the e-e interactions can be symbolized by L (ML) and S(MS)! ii) Atomic spectral terms: physical meaning (energy state of an electronic configurations that contain one to several microstates). derivation of terms for a given electronic configuration (normally simple) containing equivalent electrons and/or nonequivalent electrons. Pauli exclusion and Hund’s rules, and derivation of the ground-state term for a given electronic configuration. 2.7 计算Li2+的 所描述状态的能量E、角动量L2的平均值 要点：1）类氢离子能量及角动量本征方程表达式;2)本征函数正交归一性；3）态叠加原理；4）求平均值方法。 解： ?nlm均为Li2+原子轨道波函数（本征函数）, ?1 和?2