The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China.
J Chem Phys. 2012 Jan 7;136(1):014302. doi: 10.1063/1.3673540.
Using ab initio calculations, we have studied the structures, properties, and nature of halogen bonds in H(2)CS-XY (XY = FF, ClF, ClCl, BrF, BrCl, and BrBr) complexes. The results show that the ring-shaped complexes are formed by a halogen bond (S···X) and a secondary hydrogen bond (H···X). We also analyzed the H(2)CS-ClF-ClF and FCl-H(2)CS-ClF complexes to investigate the cooperative and diminutive halogen bonding. The cooperative effect of halogen bonding is found in the former, while the diminutive effect is present in the latter. We finally considered the solvent effect on the halogen bond in H(2)CS-BrCl complex and found that the solvent has a prominent enhancing effect on it. The complexes have also been analyzed with natural bond orbital, atoms in molecules, and symmetry adapted perturbation theory method.
利用从头算方法，我们研究了 H(2)CS-XY（XY = FF、ClF、ClCl、BrF、BrCl 和 BrBr）复合物中卤键的结构、性质和本质。结果表明，环状复合物是由卤键（S···X）和次级氢键（H···X）形成的。我们还分析了 H(2)CS-ClF-ClF 和 FCl-H(2)CS-ClF 复合物，以研究协同和削弱卤键。前者存在卤键的协同效应，而后者则存在削弱效应。最后，我们考虑了溶剂对 H(2)CS-BrCl 复合物中卤键的影响，发现溶剂对其有显著的增强作用。我们还使用自然键轨道、分子中的原子和对称适应微扰理论方法对复合物进行了分析。
