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用理论方法研究了复合物HCHO…HNO,HCOOH…HNO,HCHO…NH3,HCOOH…NH3, HCHO…NH2F和HCOOH…NH2F分子间氢键．在MP2／6-31+G(d,p),MP2／6-311++G(d,p),B3LYP／6-31+G(d,p)和B3LYP／6-311++G(d,p)水平上,利用标准方法和均衡校正方法对6种复合物进行了几何优化和振动频率计算．计算结果表明:在复合物HCHO…HNO和HCOOH…HNO中,HNO中N-H键强烈收缩,存在显著的N-H…O蓝移氢键．在复合物HCHO…NH3,HCOOH…NH3, HCHO…NH2F和HCOOH…NH2F中,NH3和NH2F中N-H键伸长,存在N-H…O红移氢键．利用自然键轨道(NBO)分析表明,电子供体轨道和电子受体轨道之间相互作用的稳定化能、电子密度重排、轨道再杂化和结构重组是决定氢键红移和蓝移的主要因素．其中,轨道间稳定化能属于键伸长效应,电子密度重排、轨道再杂化和结构重组属于键收缩效应．在复合物HCHO…HNO和HCOOH…HNO中,由于键收缩效应处于优势地位导致N-H…O蓝移氢键存在．在复合物HCHO…NH3,HCOOH…NH3,HCHO…NH2F和HCOOH…NH2F中,键伸长效应居于主导地位, N-H…O红移氢键出现．
The hydrogen bonds between the complexes HCHO ... HNO, HCOOH ... HNO, HCHO ... NH3, HCOOH ... NH3, HCHO ... NH2F and HCOOH ... NH2F were studied theoretically. In MP2 / 6-31 + G (d, p), MP2 / 6-311 ++ G (d, p), B3LYP / 6-31 + G (d, p) and B3LYP / 6-311 ++ G d, p), the geometrical optimization and vibration frequency calculation of six kinds of complexes were performed by using standard methods and equalization methods. The calculated results show that the N-H bond in HNO strongly shrinks in the complexes HCHO ... HNO and HCOOH ... HNO, and there is a significant N-H ... O blue shift hydrogen bond. In complexes HCHO ... NH3, HCOOH ... NH3, HCHO ... NH2F and HCOOH ... NH2F, N-H bonds in NH3 and NH2F elongate, leaving N-H ... O red-shifted hydrogen bonds. The analysis of NBO shows that the energy of the interaction between the electron donor orbitals and the electron acceptor orbitals, electron density rearrangement, orbital recombination and structural recombination determine the hydrogen bond redshift and blue shift major factor. Among them, the orbital stabilization can belong to the key elongation effect, electron density rearrangement, orbital recombination and structural reorganization belong to the key shrinkage effect. In the complexes HCHO ... HNO and HCOOH ... HNO, the N-H ... O blue shift hydrogen bond exists due to the predominance of the bond shrinkage effect. In the complexes HCHO ... NH3, HCOOH ... NH3, HCHO ... NH2F and HCOOH ... NH2F, the key elongation effect dominates, N-H ... O redshift hydrogen bonds appear.