Generalized approximation to the reaction path: the formic acid dimer case

A set of mass-weighted internal coordinates was derived and applied to the double proton transfer reaction in the formic acid dimer (FAD). The coordinate set was obtained starting from the Hirschfelder "mobile" by an optimization procedure consisting of a sequence of kinematic rotations. In FAD, the optimization procedure leads to three coordinates that do change significantly along the reaction path. These coordinates span the reaction space, whereas the remaining modes are treated in a harmonic approximation. The effect that the dimer dissociative motion has on the ground and excited vibrational states dynamics was explored. In the frequency region corresponding to the symmetric OH-stretch vibration four doublets have been identified with splittings of 2.76, 0.07, 0.60, and 4.03 cm(-1).