Quasidiabatic states for intramolecular charge transfer. Application to the protonation of NH3

摘要

We have constructedabinitioadiabatic and quasidiabatic surfaces for the description of the protonation of NH3. For the diabatic states, we applied a recently developed method which is based on the propagation along the reaction coordinate, starting from the dissociation region, of the maximized nonorthonormal overlap between diabatic states calculated at successive geometries. In agreement with earlier calculations lsqb;Kaldoretal., J. Chem. Phys.90, 6395 (1989)rsqb;, it was found that the adiabatic surfaces cannot explain this chargehyphen;transfer process. On the contrary, a single diabatic potential curve correlates smoothly the ground state of NH+4with the NH3+H+limit.