Please use this identifier to cite or link to this item: http://nopr.niscair.res.in/handle/123456789/31673
Title: Theoretical studies on H–M∙∙∙π (M=H, Li, Na, K) interactions involving the π-electron donors, C2H2, C2H4 and C6H6
Authors: Xie, Jiang-Bo
Li, Qiao-Ling
Shi, Wen-Jing
Ren, Fu-de
Song, Hui
Keywords: Theoretical chemistry;Noncovalent interactions;Reduced density gradient;Intermolecular interactions;Electron density
Issue Date: 11-Jun-2015
Publisher: NISCAIR-CSIR, India
Abstract: The intermolecular H–M∙∙∙π (M=H, Li, Na, K) interactions involving the π-electron donors C2H2, C2H4 and C6H6 have been investigated using the DFT-B3LYP, MP2(full) and M06-2X methods with the 6-311++G(3df,2p) basis set. A comparison with the M∙∙∙π interaction in the corresponding M∙∙∙π complex has also been carried out. The results show that the H–M∙∙∙π interaction energies follow the orders: HLi∙∙∙π > HNa∙∙∙π > HK∙∙∙π >> HH∙∙∙π and HM∙∙∙C6H6 > HM∙∙∙C2H4 ≈ HM∙∙∙C2H2. The H–M∙∙∙π interaction is stronger than the M∙∙∙π interaction. The analyses of the natural bond orbital, atoms in molecules and electron density shifts reveal the nature of the H–M∙∙∙π interactions and explain why C6H6 can form stronger complexes with HM. The reduced density gradient analysis indicates that except for the H–Li∙∙∙π and Li∙∙∙π interactions, there is no clear distinction of bonding nature between the H–M∙∙∙π and M∙∙∙π interactions. In the Li∙∙∙π complexes, an unusual green RDG isosurface appears above the Li atom, like a “cap” on the Li atom.
Page(s): 709-719
URI: http://hdl.handle.net/123456789/31673
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections: IJC-A Vol.54A(06) [June 2015]

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