论文标题
非常强大的chalcogen键：分子中的氧气是否能够形成？第一原则的观点
Very strong chalcogen bonding: Is oxygen in molecules capable of forming it? A First Principles Perspective
论文作者
论文摘要
在非共价化学文献中，人们认为i）分子中的o原子不能形成chalcogen键，而ii）如果形成，这种键非常弱。我们在这项研究中表明，这些观点不一定是正确的，因为在某些分子的氧原子和在一系列34个离子 - 分子络合物中检查的几个富含电子的富含电子阴离子碱之间的能量因弱（Ca -2.30 kcal/mol）而异（ca -2.30 kcal/mol）到Ultrastrong（-90.10 kcal/mol）。发现其中几种配合物的[MP2/Aug-CC-PVTZ]结合能与众所周知的氢键复合物[FH ... F] [FH ... F] - （大约-40 kcal/mol）相当或明显大。使用分子中的原子量子理论，二阶自然键轨道和对称自适应扰动理论能量分解分析来检查分子间相互作用的性质。发现其中许多相互作用包括混合键合特征（离子和共价），尤其是在中度至强结合的复合物中表现出来。所有这些都可以通过与反键入轨道型供体收费转移离域的结合来解释。因此，这项研究表明，分子中共价结合的氧原子具有显着的能力，可以充当异常强的chalcogen键供体。
There are views prevalent in the noncovalent chemistry literature that i) the O atom in molecules cannot form a chalcogen bond, and ii) if formed, this bond is very weak. We have shown in this study that these views are not necessarily true since the attractive energy between the oxygen atom of some molecules and several electron rich anionic bases examined in a series of 34 ion-molecule complexes varied from the weak (ca -2.30 kcal/mol) to the ultrastrong (-90.10 kcal/mol). The [MP2/aug-cc-pVTZ] binding energies for several of these complexes were found to be comparable to or significantly larger than that of the well-known hydrogen bond complex [FH...F]- (roughly -40 kcal/mol). The nature of the intermolecular interactions was examined using the quantum theory of atoms in molecules, second order natural bond orbital and symmetric adaptive perturbation theory energy decomposition analyses. It was found that many of these interactions comprise mixed bonding character (ionic and covalent), especially manifest in the moderate to strongly bound complexes. All these can be explained by a bonding to an anti-bonding orbital type donor acceptor charge transfer delocalization. This study, therefore, demonstrates that the covalently bound oxygen atom in molecules can have a significant ability to act as an unusually strong chalcogen bond donor.
