硼、氮取代二聚苯中碳原子导致层间相互作用本质变化研究

在MP2/aug-cc-pVTZ水平下优化了二聚苯及其碳被硼、氮原子取代的几何构型;计算了这些二聚体的CCSD(T)/CBS相互作用能;并用SAPT2+/aug-cc-pVDZ分析了相互作用能成分.探索了硼、氮取代二聚苯中碳原子所导致层间相互作用本质变化.结果表明:稳定构型而言,从苯(C_6H_6)、1-氮-2-硼杂苯(BNC_4H_6)、1,3-二氮-2,4-二硼杂苯(B_2N_2C_2H_6)二聚体的平行移位(PD)构型向无机苯(B_3N_3H_6)二聚体的夹心(S)构型转变,其中C_6H_6和B_3N_3H_6二聚体稳定构型的堆叠型式分别与之相对应的石墨烯(GE)和六方氮化硼(h-BN)2D层间材料的堆叠型式相一致.硼、氮原子取代二聚苯中的碳原子后使其相互作用能增大,其中BNC_4H_6和B_2N_2C_2H_6二聚体的相互作用能增大较为明显.所研究体系二聚体稳定构型均以色散能为主导、静电能次之、诱导能相对较小.硼、氮取代二聚苯中碳原子后其静电能对总吸引能的贡献明显增大.

The Nature of Interlayer Interaction of the Benzene Dimers and Their Carbons Substituted by Boron and Nitrogen Atoms

In order to explore the nature of the interlayer interaction for benzene dimers and their carbons substituted by boron and nitrogen atoms, the structures of dimers were optimized at the MP2/aug-cc-pVTZ level, and the interaction energies were calculated employing the CCSD(T)/CBS, and the energy component analysis was carried out at the SAPT2+/aug-cc-pVDZ level of theory. The calculation results show that the stable configuration changes from the parallel-displaced (PD) dimers of benzene (C6H6), 1-nitro-2-borazine (BNC4H6), 1-azonia-2-boronene (B2N2C2H6) to the sandwich (S) of the borazine (B3N3H6) dimer. Moreover, the stacking types of the stable configurations of C6H6 and B3N3H6 dimers are consistent with those of the graphene (GE) and the hexagonal boron nitride (h-BN) 2D interlayer materials, respectively. After the carbons of benzene dimers substituted by boron and nitrogen, the interaction energies have been increased, especially BNC4H6 and B2N2C2H6 dimers are most obviously. The stable configurations of dimers in the studied system are dominated by dispersion energy, followed by electrostatic energy, and the induction term are relatively inconspicuous. But it''s worth noting that the electrostatic energy contributed to total attractive energy has increased after boron and nitrogen substituting for the carbon of benzene dimer.