Weak interaction between CH3SO and HOCl: Hydrogen bond, chlorine bond and oxygen bond

• Published in: Chinese science bulletin Vol. 54; no. 17; pp. 3014 - 3022
• Main Authors: Li, ZhiFeng, Li, HongYu, Liu, YanZhi, Shi, XiaoNing, Tang, HuiAn
• Format: Journal Article
• Language: English
• Published: Heidelberg SP Science in China Press 01.09.2009
• Subjects: Articles/Physical Chemistry; Chemistry/Food Science; Earth Sciences; Engineering; Humanities and Social Sciences; Life Sciences; multidisciplinary; Physics; Science; Science (multidisciplinary); oxygen bond; HOCl; CH; AIM; chlorine bond; NBO; SO; hydrogen bond
• ISSN: 1001-6538; 1861-9541
• DOI: 10.1007/s11434-009-0477-8

B3lyp/6–311++g ** and mp2/6–311++g ** calculations were used to analyze the interaction between CH 3 SO and HOCl. Nine (complex A: S1A–S9A) and five (complex B: S4B–S7B and S10B) minima were localized on the potential energy surface of CH 3 SO⋯HOCl complexes at b3lyp/6–311++g ** and mp2/6–311++g ** computational levels, respectively. The AIM and NBO theories were also applied to explain the nature of the complexes. Bonding energy of complexes A and B corrected with BSSE falls in the ranges of −0.4–−41.4 kJ·mol −1 and −6.9–−35.8 kJ·mol −1 at mp2/6–311++g ** level, respectively. The results show that a novel oxygen bond complex (S6) exists in the system, besides hydrogen bond and chlorine bond. Especially, S6B −F , S6B −Br and S7B are blue shifted complexes compared with red shifted S6A, because the electron transfer occurs between LP 1 (S8) and σ * (O5-Cl7), resulting in the increase of O5-Cl7 and the decrease of vibrational frequency. The complex of S10B has characteristics of both red shift and blue shift.