Structural Correlations in Liquid Water: A New Interpretation of IR Spectroscopy

We present a new and alternative interpretation of the structure of the IR vibrational mode (ν(OH) band) of pure water. The re-interpretation is based on the influence of the cooperative hydrogen bonding arising from a network of hydrogen bonds in the liquid. The ν(OH) band has six components that are dominated by differences in their O−H bond lengths but deviate from thermodynamically average values due to interactions with the hydrogen bond network. The physical origin of the structure in the ν(OH) band is directly related to the O−H bond length, and variations in this bond length are caused by the influence of the surrounding hydrogen-bonded network of water molecules.