Equilibrium solvent effect in the framework of density functional theory. Application to the study of the thermodynamics of some organic and inorganic tautomeric equilibria

✍ Scribed by Carlo Adamo; Francesco Lelj

• Publisher: Elsevier Science
• Year: 1994
• Tongue: English
• Weight: 636 KB
• Volume: 223
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(94)00409-9

✦ Synopsis

As a first step toward a detailed study of solvent effects on inorganic reaction mechanisms, we have introduced the selfconsistent 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 (NHs)50N0]2+, to pentaamminenitrocobalt (III)

ion [ CO( NI-Is ) sN02] *+. This process was studied in detail experimentally, but there is a lack of theoretical characterization.

Oui results indicate the nitrite as the most stable form in aqueous solution, in agreement with experiment.