On the Nature of Bonding in Lone Pair ...pi-Electron Complexes: CCSD(T)/Complete Basis Set Limit Calculations

0327935 - ÚOCHB 2010 RIV US eng J - Journal Article
Ran, Jiong - Hobza, Pavel
On the Nature of Bonding in Lone Pair ...pi-Electron Complexes: CCSD(T)/Complete Basis Set Limit Calculations.
Journal of Chemical Theory and Computation. Roč. 5, č. 4 (2009), s. 1180-1185. ISSN 1549-9618. E-ISSN 1549-9626
R&D Projects: GA MŠMT LC512; GA AV ČR IAA400550510
Institutional research plan: CEZ:AV0Z40550506
Keywords : lone pair...pi-electron complexes * nature of bonding * CCSD(T)/ complete basis set limit calculations
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 4.804, year: 2009

Abstract: The nature of the stabilization in lone pair ...pi-electron complexes was investigated using the highly accurate CCSD(T) method based on the complete basis set limit, as well as theDFT-SAPTperturabativemethod.Specifically,westudiedvariousstructures ofbenzene ... water, benzene ... dimethylether, and 1,2,4,5-tetracyanobenzene ... water complexes. The lone pair ...pi- electron interactions between an unsubstituted aromatic ring and a water molecule are repulsive in the whole range of vertical distances. Partial stabilization results by rotating the water molekule by 90(with the water and aromatic ring being localized in parallel planes) or by decreasing the negative charge at oxygen and simultaneously increasing the polarizability of the system, which provides stabilization even for genuine lone pair ...pi-electron interactions. In these cases, a substantial part of the stabilization stems from dispersion energy.
Permanent Link: http://hdl.handle.net/11104/0174360