Theoretical Study on Structures and Properties of N 2 O···HOCl Complexes

• Published in: Chinese journal of chemistry Vol. 27; no. 5; pp. 900 - 906
• Main Authors: YUAN, Ku, LIU, Yanzhi, MA, Weichao, TANG, Huian, ZHU, Yuancheng, ZHANG, Ji
• Format: Journal Article
• Language: English
• Published: 01.05.2009
• ISSN: 1001-604X; 1614-7065
• DOI: 10.1002/cjoc.200990152

Abstract B3LYP/6‐311++G∗︁∗︁ and MP2/6‐311++G∗︁∗︁ calculations were used to analyze the interaction between hypochlorous acid (HOCl) and nitrous oxide (N 2 O). The results showed that there are six and four equilibrium geometries at the B3LYP/6‐311++G∗︁∗︁ and MP2/6‐311++G∗︁∗︁ computational levels, respectively. The equilibrium geometries of S1 and S3 were confirmed to be transition states by analytical frequency computations, and the other equilibrium geometries as minima. Complexes of S3 , S5 and S6 use the H(6) atom of HOCl as a proton donor and the terminal O(3) atom of N 2 O as an acceptor. However, S2 uses the terminal N(1) atom of N 2 O as an acceptor. As for S1 and S4 , S1 uses the Cl(4) atom of HOCl as a proton donor and the terminal N(1) atom of N 2 O as an acceptor; S4 uses the terminal O(3) atom of N 2 O as an acceptor. Interaction energy of the complexes corrected with basis set superposition error (BSSE) lies in the range of −1.56–−8.73 kJ·mol −1 at the B3LYP/6‐311++G∗︁∗︁ levels. The natural bond orbit (NBO) and atoms in molecules (AIM) theory were also applied to explain the structures and the properties of the complexes.