Acta Phys. -Chim. Sin. ›› 2008, Vol. 24 ›› Issue (09): 1625-1630.doi: 10.1016/S1872-1508(08)60068-6

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Structures and Electronic Properties of HOCl…HCOCl Complexes

LIU Yan-Zhi, HE Li-Hong, YUAN Kun, LV Ling-Ling, WANG Yun-Pu   

  1. College of Life Science and Chemistry, Tianshui Normal University, Tianshui 741000, Gansu Province, P. R. China; College of Chemistry&Chemical Engineering, Northwest Normal University, Lanzhou 730070, P. R. China
  • Received:2008-03-13 Revised:2008-05-24 Published:2008-09-10
  • Contact: LIU Yan-Zhi

Abstract: B3LYP/6-311++G** and MP2/6-311++G** calculations were used to analyze the interaction between hypochlorous acid (HOCl) and formyl chloride (HCOCl). The results showed that there were four equilibriumgeometries (S1, S2, S3, and S4) optimized at B3LYP/6-311++G** level, and all the equilibrium geometries were confirmed to be in stable states by analytical frequency calculations. Complexes S1 and S3 use the 5H atom of HOCl as proton donor and the terminal 1O atom of HCOCl as acceptor to form red shift hydrogen bond systems. However, the blue-shifted hydrogen bond (2C—3H…6O) coexists with 4Cl…5Ointeraction in structures S2. As for S4, it uses the 7Cl atomofHOCl as proton donor and the terminal 1O atom of HCOCl as acceptor to form red shift halogen bond system. Interaction energies between monomers in the four complexes corrected with basis set superposition error (BSSE) and zero-point vibrational energy (ZPVE) lie in the range from -5.05 to -14.76 kJ·mol-1 at MP2/6-311++G** level. The natural bond orbital (NBO) and atoms in molecules (AIM) theories have also been applied to explain the structures and the properties of the complexes.

Key words: Hypochlorous acid, Formyl chloride, Noncovalent interaction, NBO theory, AIMtheory


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