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化学学报
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化学学报 ›› 1995, Vol. 53 ›› Issue (1): 14-19. 上一篇    下一篇

研究论文

含氮D-A加合物的自然杂化轨道研究

李林峰;方维海;游效曾   

  1. 南京大学配位化学研究所;南京大学配位化学国家重点实验室
  • 发布日期:1995-01-15

Natural hybrid orbital analyses on D-A adducts of ammonia and various acceptors

LI LINFENG;FANG WEIHAI;YOU XIAOZENG   

  • Published:1995-01-15

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496

采用无参数Fenske-Hall资洽场分子轨道方法计算了氨的三类给予-接受型(D-A)加合物:氢键和锂键型H~3N-AX(A=H,Li;X=F,CI).孤对-空位型H~3N-BX~3(X=H,F,CI,Br)和孤对-σ型H~3N-XX'(X,X'=F,CI)的电子结构. 利用所得波函数对上述体系进行了自然杂轨道分析,给出了三类加合物D-A作用的定域图象. 将分子价的概念推广D-A作用体系的研究,结果表明,在形成D-A加合物时,氨分子价的增量与D-A作用强度呈单调变化,进而提出了用分子价来衡量加合物中D-A相互作用的强弱, 指出了它们相互作用的共通特征在于使分子价的不饱和性得到补偿.

关键词: 氨, 电子结构, 氢键, 加合物, 锂键, 自然杂化轨道, 分子价

Parameter-free Fenske-Hall SCF MO method was used to calculate the electronic structures of three kinds of D-A complexes of ammonia: H3N-AX (A = H, Li; X = F, Cl); H3N-BX3 (X = H and halogen) and H3N-XX' (X, X' = F, Cl). Based on the wave functions thus obtained, natural hybrid orbital anal. was carried out. Mol. valency was introduced and computed, which show that the valency increments of ammonia vary monotonically with the interaction intensities between acceptor (A) and donor (D) in a series of adducts. Moreover, our calculation also demonstrates that the nature of D-A interaction can be interpreted in terms of the unsatn. of mol. valency.

Key words: AMMONIA, ELECTRONIC STRUCTURE, HYDROGEN BONDS, ADDITION COMPOUNDS, LITHIUM BOND

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