Ab initio theoretical study of the monomer-dimer equilibrium in lithium and sodium gem-difluoro allyl and methyl systems

✍ Scribed by Carlo Canepa; Paola Antoniotti; Glauco Tonachini

• Book ID: 104203218
• Publisher: Elsevier Science
• Year: 1994
• Tongue: French
• Weight: 727 KB
• Volume: 50
• Category: Article
• ISSN: 0040-4020
• DOI: 10.1016/s0040-4020(01)85290-x

✦ Synopsis

Non-empirical calculations on lithium and sodium gem-difluoroallyl and dlfhmromethyl systems show that the monomerdimer equilibrium is shifted in favour of the dimeric species. The two dlfluoromethyl systems show geometric and energetic features very close to those found in the larger systems. Difluoromethyl ls then used as a model for difluoroallyl to allow the investigation of the shctural and energetic effects of the interaction of a discrete number of water molecules (used to model ether molecules) with the counterion in both monomers and dlmers. Two dimerization pmceases were investigated, in which the two cations present in the dimers are surrounded by a different number of solvent moleculea.

The dlmerization energies obtained by taking into account the oxygen-cation interactloos are significantly reduced, but the equilibrium ls still estlmated to lle in favour of the dlleric specie%