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Elsevier, Chemical Physics Letters, 3-4(371), p. 267-275

DOI: 10.1016/s0009-2614(03)00255-0

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Internal rotation of disilane and related molecules: a density functional study

This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

DFT calculations performed on Si_2H_6, Si_2F_6, Si_2Cl_6, and Si_2Br_6 are reported. The evolution of the energy, the chemical potential and the molecular hardness, as a function of torsion angle, is studied. Results at the DFT-B3LYP/6-311++G** level show that the molecules always favor the stable staggered conformations, with low but significant energy barriers that hinder internal rotation. The chemical potential and hardness of Si_2H_6 remains quite constant as the sylil groups rotate around the Si-Si axis, whereas the other systems exhibit different degrees of rearrangement of the electronic density as a function of the torsion angle. A qualitative analysis of the frontier orbitals shows that the effect of torsional motion on electrophilic attack is negligible, whereas this internal rotation may generate different specific mechanisms for nucleophilic attack. ; Comment: LATeX file, 7 figures, uses elsart.cls, natbib, graphicx