Catalytic and bulk solvent effects on proton transfer: Formamide as a case study

Structural, thermodynamic, and kinetic aspects of the tautomerization of formamide through direct and solvent-assisted proton transfer have been investigated. Both specific and bulk effects of the solvent play a role in determining the overall result so that only a mixed discrete-continuum model is sufficiently reliable. Structural modifications induced by the solvent are significant, but have only a slight effect on thermodynamic and kinetic quantities. The same remarks apply to the vibrational shifts induced by the solvent.