Complete experimental rovibrational eigenenergies of HCN up to 6880 cm(-1) above the ground state

The [H,C,N] molecular system is a very important model system to many fields of chemical physics and the experimental characterization of highly excited vibrational states of this molecular system is of special interest. This paper reports the experimental characterization of all 3822 eigenenergies up to 6880 cm(-1) relative to the ground state in the HCN part of the potential surface using high temperature hot gas emission spectroscopy. The spectroscopic constants for the first 71 vibrational states including highly excited bending vibrations up to v(2) = 10 are reported. The perturbed eigenenergies for all 20 rotational perturbations in the reported eigenenergy range have been determined. The 11,070 eigenenergies up to J = 90 for the first 123 vibrational substates are included as supplement to this paper. We show that a complete ab initio rovibrational analysis for a polyatomic molecule is possible. Using such an analysis we can understand the molecular physics behind the Schrödinger equation for problems for which perturbation theoretical calculations are no more valid. We show that the vibrational structure of the linear HCN molecule persists approximately up to the isomerization barrier and only above the barrier the accommodation of the vibrational states to the double well structure of the potential takes place.