Three types of noncovalent interactions studied between pyrazine and XF.

Abstract

Three types noncovalent interactions (type I, II and III) between pyrazine (C4H4N2) and XF (X = F, Cl, Br, and I) have been discovered at the MP2/aug-cc-pVTZ level. TypeI is σ-hole interaction between the positive site on the halogen X of XF and the negative site on one of the pyrazine nitrogens. Type II is counterintuitive σ-hole interaction driven by polarization between the positive site on the halogen X of XF and a portion of the pyrazine ring. Type III is an interaction between the lateral regions of the halogen X of XF and the position of the pyrazine ring. Through comparing the calculated interaction energy, we can know that the type II and type III interactions are weaker than the corresponding type I interactions, and type III interactions are weaker than the corresponding type II interactions in C4H4N2-XF complexes. SAPT analysis shows that the electrostatic energy are the major source of the attraction for the type I (σ-hole) interactions while the type III interactions are mainly dispersion energy. For the type II (counterintuitive σ-hole) interactions in C4H4N2-XF (X = F and Cl) complexes, electrostatic energy are the major source of the attraction, while in C4H4N2-XF (X = Br and I) complexes, the electrostatic term, induction and dispersion play equally important role in the total attractive interaction. NBO analysis, AIM theory, and conceptual DFT are also being utilized.