单电子近似的理论基础.pptVIP

energy as a function of the one electron density, ? nuclear-electron attraction, electron-electron repulsion Thomas-Fermi approximation for the kinetic energy Slater approximation for the exchange energy Thomas-Fermi Model Thomas-Fermi model (semiclassical): 1927 Electron density of a uniform electron gas: Fermi wavevector and electron kinetic energy of a uniform electron gas Thomas-Fermi Model We may assume that the kinetic energy of the electron gas depends on the local electron density: The total kinetic energy of electrons in the system is therefore a functional of electron density: The Perdew-Zunger Parameterization And the Uniform Electron Gas Result The Perdew-Zunger Parameterization of The Exchange-Correlation Energy (LDA) Exchange And Correlation Energies: LDA vs. Uniform Electron Gas 理论体系 交换相关泛函、含时密度泛函、动力学平均场、密度泛函微扰理论 数值方法 基组、格点、线性标度 应用 物理、化学、生物、材料、纳米科学、光谱学 Part I: 理论体系 LDA underestimates Ec but overestimates Ex, resulting in unexpectedly good values of Exc. The LDA has been applied in, calculations of band structures and total energies in solid-state physics. In quantum chemistry,it is much less popular, because it fails to provide results that are accurate enough to permit a quantitative discussion of the chemical bond in molecules. Any real system is spatially inhomogeneous, it has a spatially varying density n(r), it would clearly be useful to also include information on the rate of this variation in the functional. In this approximation ,one tries to systematically calculate gradient-corrections of general functions of n(r) and ?n(r) Different GGAs differ in the choice of the function f(n,?n). GGAs used in quantum chemistry typically proceed by fitting parameters to test sets of selected molecules. Nowadays the most popular GGAs are PBE in physics, and BLYP in chemistry. Current GGAs seem to give reliable results for all main types of chemical bonds (covalent, ionic, metallic and hydrogen bridge). In a