High‐resolution near‐infrared spectroscopy of water dimer

High‐resolution near‐infrared spectra are reported for all of the O–H stretch vibrational bands of the water dimer. The four O–H vibrations are characterized as essentially independent proton‐donor or proton‐acceptor motions. In addition to the rotational and vibrational information contained in these spectra, details are obtained concerning the internal tunneling dynamics in both the ground and excited vibrational states. These results show that for tunneling motions which involve the interchange of the proton donor and acceptor molecules, the associated frequencies decrease substantially due to vibrational excitation. The predissociation lifetimes for the various states of the dimer are determined from linewidth measurements. These results clearly show that the predissociation dynamics is strongly dependent on the tunneling states, as well as the Ka quantum number, indicating that the internal tunneling dynamics plays an important role in determining the dissociation rate in this complex.

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