量子化学简介1113.ppt

量子化学简介 量子化学是用量子力学原理和方法研究分子微观结构以及与物质的物理和化学性质关系的一门边缘学科。在它过去多年的发展过程中，建立了一系列理论和计算方法，概括出许多对化学发展有重要意义的概念和规律。特别是七十年代以来，随着计算机技术的发展，量子化学已进入一个新的发展阶段，其研究成果使人们对物质结构与性质的内部联系以及化学现象本质与规律性的认识大大深化了。 理论方法 从头算分子轨道理论（Ab Initio Molecular Orbital Theory） 半经验的分子轨道理论（Semi-Empirical Molecular Orbital Theory） 密度泛函理论（Density Functional Theory) Schr?dinger equation: E ? = H ? Schr?dinger equation: Schr?dinger equation after Born-Oppenheimer Approximation Simplifying assumptions are employed to ‘solve’ the Schr?dinger equation approximately: Born-Oppenheimer approximation allows separate treatment of nuclei and electrons Hartree-Fock independent electron approximation allows each electron to be considered as being affected by the sum (field) of all other electrons. LCAO Approximation Born-Oppenheimer Approx. States that electron motion is independent of nuclear motion, thus the energies of the two are uncoupled and can be calculated separately. Derives from the large difference in the mass of nuclei and electrons, and the assumption that the motion of nuclei can be ignored because they move very slowly compared to electrons Htot a (Tn) + Te + Vne + Vn + Ve Kinetic energy Potential energy (Tn is omitted; this ignores relativistic effects, yielding the electronic Schr?dinger equation.) Assumes that each electron experiences all the others only as a whole (field of charge) rather than individual electron-electron interactions. Introduces a Fock operator F: F???????? which is the sum of the kinetic energy of an electron, a potential that one electron would experience for a fixed nucleus, and an average of the effects of the other electrons. LCAO Approximation Electron positions in molecular orbitals can be approximated by a Linear Combination of Atomic Orbitals. This reduces the problem of finding the best functional form for the molecular orbitals to the much simpler one of optimizing a set of coefficients (cn)