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采用MP2/aug-cc-p VDZ(对于Xe和I原子采用aug-cc-p VDZ-PP基组)优化了复合物HXe Br…C_6H_5X(X=H,CH_3,NH_2,N(CH_3)_2,NHCH_3,OH,OCH_3,CN,F,Cl,Br,I,COOH,SO_3H,CF3)及单体的几何构型,详细分析了π…H键和双齿氢键两种弱相互作用类型的特征,以及不同的取代基对这两种弱相互作用能的影响.对14个双齿氢键型复合物,我们发现复合物的相互作用能与苯环衍生物(C_6H_5X)的偶极矩,复合物中Xe—Br键键长的变化,H—Xe键键长的变化和H—Xe键振动频率的变化,以及双齿氢键上Br原子和两个H原子范德华表面相互穿透距离之和均有较好的线性关系.另外,我们还发现复合物的相互作用能与双齿氢键上两个键临界点的电子密度之和,电子密度Laplacian值之和,静电势之和,以及双齿氢键和苯环碳原子形成环的环临界点处的电子密度,电子密度Laplacian值以及静电势均有着较好的线性关系.
The complexes HXeBr ... C_6H_5X (X = H, CH_3, NH_2, N (CH_3) _2, H_3H_5X_3) were optimized using the MP2 / aug-cc-p VDZ (augmented with the aug- cc-p VDZ-PP basis set for Xe and I atoms) NHCH_3, OH, OCH_3, CN, F, Cl, Br, I, COOH, SO_3H, CF3) and the geometrical configurations of the monomers. The characteristics of two weak interaction types of π ... H and bidentate hydrogen bonds , As well as the effects of different substituents on these two weak interactions.For the 14 bidentate hydrogen-bonding complexes, we found that the interaction between the complexes and the dipole moments of the benzene ring derivatives (C_6H_5X) The change of Xe-Br bond length, the change of H-Xe bond length and the vibrational frequency of H-Xe bond, and the sum of the mutual penetration distance of Br atom and two H atom van der Waals surfaces on the double-dentate hydrogen bond In addition, we also found that the interaction between the complexes can be related to the sum of the electronic densities of the two bonds on the double-dentate hydrogen bonds, the sum of the electron density Laplacian values, the electrostatic potentials, and the double The electron density, the electron density Laplacian value and the electrostatic potential at the critical point of the ring formed by the hydrogen bonding of benzene ring and the benzene ring carbon atom have a good linear relationship.