A diverse set of 100 chalcogen-bonded complexes comprising neutral, cationic, anionic, divalent, and double bonded chalcogens has been investigated using ωB97X-D/aug-cc-pVTZ to determine geometries, binding energies, electron and energy density distributions, difference density distributions, vibrational frequencies, local stretching force constants, and associated bond strength orders. The accuracy of ωB97X-D was accessed by CCSD(T)/aug-cc-pVTZ calculations of a subset of 12 complexes and by the CCSD(T)/aug-cc-pVTZ //ωB97X-D binding energies of 95 complexes. Most of the weak chalcogen bonds can be rationalized on the basis of electrostatic contributions, but as the bond becomes stronger, covalent contributions can assume a primary role in the strength and geometry of the complexes. Covalency in chalcogen bonds involves the charge transfer from a lone pair orbital of a Lewis base into the σ* orbital of a divalent chalcogen or a π* orbital of a double bonded chalcogen. We describe for the first time a symmetric chalcogen-bonded homodimer stabilized by a charge transfer from a lone pair orbital into a π* orbital. New polymeric materials based on chalcogen bonds should take advantage of the extra stabilization granted by multiple chalcogen bonds, as is shown for 1,2,5-telluradiazole dimers.

中文翻译：

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硫属元素键合的许多方面：振动光谱法描述。

已使用ωB97X-D/ aug-cc-pVTZ研究了包含中性，阳离子，阴离子，二价和双键硫属元素的100种硫族元素键合复合物的不同集合，以确定几何形状，结合能，电子和能量密度分布，差密度分布，振动频率，局部拉伸力常数以及相关的粘结强度顺序。通过CCSD（T）/ aug-cc-pVTZ对12个配合物的子集的计算以及CCSD（T）/ aug-cc-pVTZ //ωB97X-D的95个配合物的结合能来获得ωB97X-D的准确性。大多数弱硫族元素键都可以在静电作用的基础上合理化，但是随着键变得更强，共价作用可以在配合物的强度和几何形状中起主要作用。硫族元素键的共价性涉及从路易斯碱的孤对轨道到二价硫族元素的σ*轨道或双键硫族元素的π*轨道的电荷转移。我们首次描述了通过从孤对轨道到π*轨道的电荷转移稳定的对称硫族元素结合的同型二聚体。如1,2,5-telluradiazole二聚体所示，基于硫属元素键的新型聚合物材料应利用多个硫属元素键所赋予的额外稳定性。