EQUILIBRIUM SOLVENT EFFECT IN THE FRAMEWORK OF DENSITY-FUNCTIONAL THEORY - APPLICATION TO THE STUDY OF THE THERMODYNAMICS OF SOME ORGANIC AND INORGANIC TAUTOMERIC EQUILIBRIA

As a first step toward a detailed study of solvent effects on inorganic reaction mechanisms, we have introduced the self-consistent reaction field in a density functional scheme. To test our results, we have studied the thermodynamics of the tautomerization reactions of formamide and 2-pyridone, for which several experimental and theoretical works are available. Our results are in agreement with experimental results and sophisticated ab initio computations. As a further application, we have studied the linkage isomerization of pentaamminenitritocobalt (III) ion, [Co(NH3)5O2NO]2+, to pentaamminenitrocobalt (III) ion, [CO(NH3)5NO2]2+. This process was studied in detail experimentally, but there is a lack of theoretical characterization. Our results indicate the nitrito as the most stable form in aqueous solution, in agreement with experiment.