双原子分子初级.pptVIP

分子轨道理论 价键理论 化学键理论 价电子离域 价电子定域在两原子之间或成为孤对电子 每个原子提供一个价电子和一个轨道重叠成键 Molecular orbital theory and diatomic molecules 分子轨道理论和双原子分子 Molecular orbital theory 分子轨道理论 a. Every electron in a molecule is in an average potential field of the nuclei and the other electrons. 每个电子围绕原子核和其他电子组成的平均势场中运动 b. 分子轨道近似为原子轨道线性组合 组成分子轨道的原子轨道满足： * have comparable energy, 能量相近 * have compatible symmetry,对称性匹配 * be able to have maximum overlap. 轨道最大重叠 n个原子轨道线性组合形成n个分子轨道 n个原子轨道线性组合形成n个分子轨道 The overlap integral S may be positive (bonding), negative (antibonding) or zero (non-bonding interaction). 2. The characteristic distribution and classification of molecular orbital 分子轨道分类 a. ?-orbital and ?-bond ?-轨道与?-键 以“头碰头”的方式重叠； 原子轨道重叠部分沿着键轴呈圆柱对称； 成键时，原子轨道发生最大重叠。 ?s ?s* ?p ?p* 2. The characteristic distribution and classification of molecular orbital 分子轨道分类 a. ?-orbital and ?-bond ?-轨道与?-键 + + - + + - + - + + - s pz ?ps ?*ps 2. The characteristic distribution and classification of molecular orbital b. ?-orbital and ?-bond ?-轨道与?-键 原子轨道平行或“肩并肩”重叠； 重叠部分对通过一个键轴的平面具有镜面反对称性； 轨道重叠程度比 ?键小，键能也小。 2. The characteristic distribution and classification of molecular orbital b. ?-orbital and ?-bond ?-轨道与?-键 3. The structure of homonuclear diatomic molecules 同核双原子分子结构 a. The ground state electronic configurations 基态电子组态 The aufbau (building-up) principle in molecules: Pauli exclusion principle Pauli不相容原理 The minimum energy priciple 能量最低原理 Hund’s rule. Hund规则 H Energy H H2 1s 1s Y+=1?g Y-=1?*u Diatomic molecules: The bonding in H2 (H2分子结构) [H2] = 1?g2 Bond order(键级) of H2+=1/2; bond order of H2=1. For H2, the stabilization energy is 432 kJ/mol. n: Electrons in bonding orbitals 成键 n*:Electrons in antibonding orbitals反键 Diatomic molecules: The bonding in He2 He also has only 1s AO, so the MO diagram for the molecule He2 can be f