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- Title
Are water–aromatic complexes always stabilized due to π–H interactions? LMP2 study.
- Authors
Reyes, Abraham; Fomina, Lioudmila; Rumsh, Lev; Fomine, Serguei
- Abstract
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 (&bond;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 <0.15 tend to form A-type complexes, while aromatic molecules with “molecular electronegativity” of <0.15 a.u. form B-type complexes. The binding energy of water–aromatic complexes undergoes a minimum in the area of switching from A-type to B type complexes, which can be rationalize in terms of frontier orbital interactions. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005
- Subjects
HYDROCARBONS; ELECTRONIC structure; PARTICLES (Nuclear physics); ORGANIC compounds; MOLECULAR orbitals; CHEMICAL bonds; QUANTUM chemistry
- Publication
International Journal of Quantum Chemistry, 2005, Vol 104, Issue 3, p335
- ISSN
0020-7608
- Publication type
Article
- DOI
10.1002/qua.20558