[化学]南京大学结构化学双语课件CH3LEC2.pptVIP

Concept of Basis Set Using Atomic Orbitals as the Basis Set Slater Orbitals The Variation Principle Proof of The Variation Principle Linear Variation Method Steps of the Linear Variation Method The Simple Molecular Orbital Theory Linear Combination of Atomic Orbitals LCAO Overlap Integral, Some Special Cases Coulomb Integral Resonance Integral Chemical Bonding between Two Atoms Chemical Bonding, Energy Level Pattern Chemical Bond Strength, Discussion Computation of Molecular Orbital Molecular Orbital (Wavefunction ) The Principles of Chemical Bonding The Principles of Chemical Bonding Relation between b ( HAB ) And S When , b = 0 , h = 0 No bonding When aA = aB , h = b Strongest bonding SAB =0 These two equations are not independent, therefore, one equation is enough for deriving the relation between ca and cb For Energy Level E+ =aA-h Define 0 ? k ? 1 For Energy Level E-=aB+h A B 0 ? k ? 1 E+ E- More contributions from B More contributions from A For any effective chemical bonding between two orbitals Principle 1 jA should be energetically similar to jB Principle 2 jA and jB should be effectively overlaped (Large b ) Principle 3 The symmetries of jA and jB with respect to the internuclear axis are adapted. So that b ? 0 * * Section 3.3 LCAO and Molecular Orbital Theory Concept of Basis Set Variation Principle and LCAO Method The Simple Molecular Orbital Theory Principles of Chemical Bonding Concept of Basis Set In 2-D space: In 3-D space: In N-D space: Here, {x, y}, {x, y, z} and {j1, j2,…, jN} are orthonormal complete set in 2-D, 3-D and N-D spaces, respectively. The Molecular Orbitals are usually approximated as Linear Combinations of a finite number of Atomic Orbitals (LCAO) e.g., The basis set can be constructed from the Slater orbitals: n* The Effective Principal Quantum Number s The Shielding Constant 2. Variation Principle and LCAO For any well-behaved function y, it