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Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts
Author(s) -
Echeverría Jorge,
Aullón Gabriel,
Alvarez Santiago
Publication year - 2017
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25432
Subject(s) - intermolecular force , chemistry , non covalent interactions , molecule , chemical physics , crystallography , atoms in molecules , silicon , electron density , computational chemistry , hydrogen bond , physics , electron , quantum mechanics , organic chemistry
In line with previous work in which we established the factors that enhance attractive CH···HC dihydrogen interactions in alkanes, an extended theoretical analysis of noncovalent intermolecular interactions in group 14 hydrides is presented here. Remarkably, these weak interactions may play a major role in determining the crystal structures adopted by several families of molecules. A combined structural and computational analysis at the MP2 level allowed us to identify and characterize different interactions of the type EH···HE and E···HE (E = Si, Ge, Sn, and Pb), and to find also the most suitable scenario for the establishment of each particular type. The nature of the interactions has been analyzed in terms of natural charges of the atoms involved and a topological analysis of the electron density of several dimers confirms the existence of H···H and H···E attractive contacts. We have observed that the interaction strength increases when descending down the periodic group and that silicon has a marked tendency to establish Si···HSi interactions. A size‐dependent backbone effect that reinforces H···H dihydrogen interactions in polyhedral systems has also been found.