Hydrogen bonding in hydrogen peroxide and water. A Raman study of the liquid state

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Abstract
The Raman spectra of pure, anhydrous H2O2 and its deuteriated analogues, D2O2 and HDO2, were examined in the liquid state up to 40 °C and supercooled down to −75 °C. The OH (OD) stretching bands show a broad, single‐peaked contour, and a strongly temperature‐dependent asymmetry‐ Decomposition by analog computer reveals two overlapping bands, about 100 cm−1 apart, with different temperature behavior. In contrast with water, there is no indication in the hydrogen peroxide spectra of ‘free,’ i.e. non‐hydrogen‐bonded, OH groups, in keeping with the flexible geometry of the molecule and its electronic configuration. Based on these spectra, and by analogy with water, a two‐state model is proposed featuring a continuum of hydrogen‐bonded H2O2 molecules, with elose‐packed OH groups in two kinds of environments. The hydrogen bonds are slightly weaker (12–15%) than those in water. Hydrogen peroxide is the best analog for studying the structure of water.

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