Publicité

Commentaire : 3.2.3 Electrochemistry The molecular structures of the neutral complexes (oxi- dized forms) and their reduced forms are optimized with a frequency calculation to confirm the energy minima. The reduction potential was calculated from the solvation-free energies. The latter was obtained by implicitly using the CPCM solvation model [86] with dichloromethane as a sol- vent in accordance with the experiment. The free energies in the gas state and the solvated state of each species were evaluated at 298.15 K and under a pressure of 1 atm. We calculated the absolute reduction potential for each complex using the Born-Haber thermodynamic cycle, given in Fig. 3, which links the different electron transfer processes in the gas and solvated phases. According to Nernst's relation:

Format du document : application/vnd.openxmlformats-officedocument.wordprocessingml.document