Coupling interactions between sulfurous acid and the hydroperoxyl radical.
Radical-molecule complexes associated with the hydroperoxyl radical (HOO) play an important role in atmospheric chemistry. Herein, the nature of the coupling interactions between sulfurous acid (H(2)SO(3)) and the HOO radical is systematically investigated at the B3LYP/6-311++G(3df,3pd) level of theory in combination with the atoms in molecules (AIM) theory, the natural bond orbital (NBO) method, and energy decomposition analyses (EDA). Eight stable stationary points possessing double H-bonding features were located on the H(2)SO(3)...HOO potential energy surface. The largest binding energies of -12.27 and -11.72 kcal mol(-1) are observed for the two most stable complexes, where both of them possess strong double intermolecular H-bonds of partially covalence. Moreover, the characteristics of the IR spectra for the two most stable complexes are discussed to provide some help for their possible experimental identification.
Li
Ping
P
Key Laboratory of Life-Organic Analysis, College of Chemistry Science, Qufu Normal University, Qufu, 273165, P. R. China. lignip@163.com
Ma
Zhi-Ying
ZY
Wang
Wei-Hua
WH
Shen
Zhi-Tao
ZT
Bi
Si-Wei
SW
Sun
Hai-Tao
HT
Bu
Yu-Xiang
YX
D006860:Hydrogen Bonding; D006861:Hydrogen Peroxide / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D013456:Sulfur Acids / Q000737:chemistry*
D013456:Sulfur Acids; D006861:Hydrogen Peroxide