Int J Quantum Chem, 2005, 104(3):335-341

Are water-aromatic complexes always stabilized due to π-H interactions? LMP2 study

Eight complexes of various aromatic molecules with water have been studied theoretically at the local Møller-Plesset 2nd order theory (LMP2)/aug-cc-pVTZ(-f)//LMP2/6-31+G* level of theory. Two types of complexes can be formed, depending on the electronic structure of aromatic molecules. Donor hydrocarbons form A-type complexes, while aromatics bearing electron-withdrawing substituents form B-type complexes. A-type complexes are stabilized due to π-H interactions with the OH bond pointing to the aromatic molecule plane, while B-type complexes have geometry with the oxygen atom pointing to the aromatic molecule plane stabilized by the interaction of highest occupied molecular orbital (HOMO) of water molecule with π* orbitals of the aromatics. It has been found that a (-HOMO-lowest unoccupied molecular orbital (LUMO)/2 value of aromatic molecule, which can be called "molecular electronegativity," is useful to predict the type of complex formed by aromatic molecule and water. Aromatic hydrocarbons with "molecular electronegativity" of

Reyes A, Fomina L, Rumsh L, Fomine S

IBCH: 1178
Ссылка на статью в журнале: http://doi.wiley.com/10.1002/qua.20558
Кол-во цитирований на 09.2023: 33
Информация пока не проверена модераторами