磷的d轨道在H_3PO分子中的作用  

On the Role of d Orbitals in H_3PO

作　　者：丁涪江[1] 吴添智[1] 江丽葵[1] 张良辅[1] 

机构地区：[1]中国科学院成都有机化学研究所,成都610041

出　　处：《化学学报》1999年第3期264-269,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(29673041)

摘　　要：用分子片轨道在分子环境中发生极化的概念研究d轨道在H_3PO分子中的作用.H_3PO分子被分为两个分子片——H_3P和O.在RHF/6-31G^(?)水平上计算出分子环境中的极化了的分子片轨道(FOM).再剔除d函数为主的FOM,用剩余的FOM为基进行构型优化,得到与RHF/6-31G^(?)相近的结果.这一结果说明磷原子的d函数在H_3PO分子中仅仅起一个极化函数的作用,而不是起价轨道作用.The role of d orbitals in the bonding of H3PO is studied using our developed method of polarized fregment orbital analysis. The whole molecule H3PO is divided into two fragments H3P and O. Then the polarized fragment orbitals in molecular environment(FOM) are calculated using 6-31G* basis set. Whole molecule is recalculated using the FOM basis set in which the d functions are deleted. The optimized P-O bond length is close to the result of RHF/6 - 31G* . The results of this study lead to a refined picture of the nature of hypervalence in H3PO. The role of d functions of phosphorus atom in the wave function of H3PO is only a polarized function just as p functions are customarily added to hydrogen atom s functions. The 'valence d orbital' role should be rejected in molecule H3PO.

关 键 词：磷原子 膦氧化物 H3PO D轨道 化学键 极化函数 

分 类 号：O627.51[理学—有机化学]