多电子波函数和运算符.ppt

Chapter 5 Many-electron wave functions and operators;5.1 The electronic problem 5.2 Orbitals, Slater determinants, and basis functions 5.3 Operators and matrix elements 5.4 Second quantization (skipped) 5.5 Spin-adapted configurations ;5.1 The electronic problem ;: the mass of the electron;Thus,; If we set ;The H atom ground-state energy:;Conversion of atomic units to SI units;The Hamiltonian for N electrons and M nuclei is; The electrons in a molecule move in the field of fixed nuclei. Thus, the kinetic energy of the nuclei can be neglected and the internuclear repulsion can be considered to be constant. ;Multiplying both sides of ; Thus, the nuclear Schr?dinger equation which describes the vibration, rotation, and translation of a molecule is: ;Figure 5.1 The potential energy curve for a typical diatomic molecule ;For diatomic molecules,;For a diatomic molecule, ;for spin functions ; ;The wave function of a system of interacting identical particles;Since the particles are indistinguishable, the two wave functions;The eigenvalue equation of the permutation operator ;For fermions (after E. Fermi) such as electrons or other particles;For electrons:;5.2 Orbitals, Slater determinants, and basis functions ;If the set of spatial orbitals;Each spatial orbital;5.2.2 Hartree products ; ; or ;Integrating over the coordinates of all electrons but electron-one:;it violates the antisymmetry principle. ;5.2.3 Slater determinants ;If both electrons occupy the same spin orbital,;For an N-electron system, if; ;Slater determinants formed from orthonormal spin orbitals are normalized. ;Consider a two-electron system,; ; ;If;(2) If the two electron have the same spin (say β), we have;not considered within the single Slater determinantal description. ; ;which determines the probability of two electrons (any two) being ;5.2.4 The Hartree-Fock approximation ;By minimizing; ; ; ;Using a basis set of;5.2.5 The minimal basis H2 model ;Figure 5.2 Coordination system