Key Laboratory of Life-Organic Analysis, College of Chemistry Science, Qufu Normal University, Qufu, 273165, P. R. China.
Chemphyschem. 2010 Feb 22;11(3):696-705. doi: 10.1002/cphc.200900781.
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.
与过氧自由基（HOO）相关的自由基分子配合物在大气化学中起着重要作用。在此，在 B3LYP/6-311++G（3df，3pd）理论水平上，结合原子分子（AIM）理论、自然键轨道（NBO）方法和能量分解分析（EDA），系统研究了亚硫酸（H2SO3）和 HOO 自由基之间的偶合相互作用的性质。在 H2SO3...HOO 势能表面上定位了具有双氢键特征的八个稳定的驻点。对于两个最稳定的配合物，观察到最大的结合能为-12.27 和-11.72 kcal mol-1，它们都具有强烈的部分共价的双分子间氢键。此外，还讨论了两个最稳定配合物的 IR 光谱特征，为它们可能的实验鉴定提供了一些帮助。
