A joint experimental and first-principles quantum chemical study of the vibration-rotation states of the water molecule up to its first dissociation limit is presented. Triple-resonance, quantum state-selective spectroscopy is used to probe the entire ladder of water's stretching vibrations up to 19 quanta of OH stretch, the last stretching state below dissociation. A new ground state potential energy surface of water is calculated using a large basis set and an all-electron, multireference configuration interaction procedure, which is augmented by relativistic corrections and fitted to a flexible functional form appropriate for a dissociating system. Variational nuclear motion calculations on this surface are used to give vibrational assignments. A total of 44 new vibrational states and 366 rotation-vibration energy levels are characterized; these span the region from 35,508 to 41,126 cm(-1) above the vibrational ground state.
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