Jabłoński Mirosław
Department of Quantum Chemistry, Faculty of Chemistry Nicolaus Copernicus University in Toruń 7-Gagarina St. 87-100 Toruń Poland.
ChemistryOpen. 2019 Apr 18;8(4):497-507. doi: 10.1002/open.201900109. eCollection 2019 Apr.
We refer to frequently used determinants suggesting dominant interactions between distant atoms in various dimers. First of all, we show, against the still-prevailling opinion, that, in general, bond paths have nothing in common with dominant intermolecular interactions and therefore they are useless in such cases. Quite the contrary, reliable information about dominant intermolecular interactions can be obtained by means of electrostatic potential maps, which very convincingly explain mutual orientation of molecules in a dimer. For the first time, numerous examples of interactions that violate both the concept of privileged exchange channels proposed by Pendás and his collaborators as well as inequalities obtained by Tognetti and Joubert for the parameter related to secondary interactions are presented. The possible cause of this violation is suggested. We also show that the so-called counterintuitive bond paths result from quite natural behavior of the electron density gradient vector, i. e. searching for those areas of space that are characterized by large values of electron density or the most expanded its distributions.
我们提及了常用于表明各种二聚体中远距离原子间主要相互作用的决定因素。首先，与仍然流行的观点相反，我们表明，一般来说，键径与主要分子间相互作用毫无共同之处，因此在这种情况下它们毫无用处。恰恰相反，关于主要分子间相互作用的可靠信息可以通过静电势图获得，静电势图非常令人信服地解释了二聚体中分子的相互取向。首次展示了大量违反彭达斯及其合作者提出的特权交换通道概念以及托涅蒂和朱伯特针对与二级相互作用相关参数得出的不等式的相互作用实例。提出了这种违反的可能原因。我们还表明，所谓的反直觉键径是由电子密度梯度向量的相当自然的行为导致的，也就是说，电子密度梯度向量会寻找那些以电子密度值大或其分布最扩展为特征的空间区域。
