Theoretical study of the 1,3-hydrogen shift of triazene in water.
The 1,3-hydrogen shift of triazene in aqueous solution was studied with a combination of QM/MM methods. First, the different species involved were characterized and the activation free-energies calculated with ASEP/MD, a method that makes use of the mean field approximation. Then the reaction dynamics was simulated with a QM/MM/MD method. A very strong influence of the solvent was observed, both specific, with the participation of a water molecule, and from the rest of the solvent. The effect of solvation on the geometry and electron distribution of triazene is important: N-N bond lengths tend to be more similar and the molecule acquires a planar structure. For the transition state structure, a substantial degree of ionic nature was found. Dynamic solvent effects were also analyzed.
Fdez Galván
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I
Departamento de Química Física, Facultad de Ciencias, Universidad de Extremadura, Avda. de Elvas s/n, 06071 Badajoz, Spain.
Aguilar
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MA
Ruiz-López
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MF