Chattaraj, Pratim K. ; Pérez, Patricia ; Zevallos, Jenny ; Toro-Labbé, Alejandro (2002) Theoretical study of the trans-N2H2→cis-N2H2 and F2S2→FSSF reactions in gas and solution phases Journal of Molecular Structure (Theochem), 580 (1-3). pp. 171-182. ISSN 0166-1280
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Official URL: http://www.sciencedirect.com/science/article/pii/S...
Related URL: http://dx.doi.org/10.1016/S0166-1280(01)00611-X
Abstract
We present a density functional theory (DFT) study of the solvent effects on two intramolecular rearrangements. We have used relative values of energy, electronic chemical potential, chemical hardness and dipole polarizability as global descriptors to analyze the trans-N2H2→cis-N2H2 and F2S2→FSSF rearrangements in gas and solution phases. Our results agree well with the maximum hardness principle and the minimum polarizability principle. Both reactions become thermodynamically and kinetically more favorable, in the condensed phase. All the species associated with these reactions become less electrophilic in the presence of a polarizable environment. The lowering in the electrophilicity of the species upon solvation may be partitioned into two contributions. The first one contains the variations in electronic chemical potential for the change of phase; whereas the second one indirectly encompasses the variations in chemical hardness through the changes in the maximum charge transfer to the environment. For both reactions, the electronic chemical potential and chemical hardness variations cooperatively contribute to the loss in the electrophilicity power from the gas to solution phase.
Item Type: | Article |
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Source: | Copyright of this article belongs to Elsevier Science. |
Keywords: | Solvent Effects; Electrophilicity Index; Reaction Hardness Profile; Reaction Electronic Chemical Potential Profile; Reaction Polarizability Profile; Reaction Energy Profile; HNNH; FSSF |
ID Code: | 71225 |
Deposited On: | 24 Nov 2011 08:38 |
Last Modified: | 24 Nov 2011 08:38 |
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