We summarize here our experimental studies of the high rovibrational energy levels of water. The use of double-resonance vibrational overtone excitation followed by energy-selective photofragmentation and laser-induced fluorescence detection of OH fragments allowed us to measure previously inaccessible rovibrational energies above the seventh OH-stretch overtone. Extension of the experimental approach to triple-resonance excitation provides access to rovibrational levels via transitions with significant transition dipole moments (mainly OH-stretch overtones) up to the dissociation threshold of the O-H bond. A collisionally assisted excitation scheme enables us to probe vibrations that are not readily accessible via pure laser excitation. Observation of the continuous absorption onset yields a precise value for the O-H bond dissociation threshold, 41 145.94 ± 0.15 cm(-1). Finally, we detect long-lived resonances as sharp peaks in spectra above the dissociation threshold.
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