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To test basic assumptions inherent to most theories of molecular liquids andglasses, Infrared spectroscopy is carried out on short polyalcohols attemperatures ranging from far above to far below their glass transition. Byanalyzing specific vibrations, the thermal expansion of covalent bonds andhydrogen bridges is determined revealing striking differences. A comparisonwith density verifies the negligibility of \textit{intra}molecular expansionbut exposes severe inhomogeneities on \textit{inter}molecular scale. Thissignals distinct roles in glassy densification and promotes an atomisticunderstanding.

Intra- and Intermolecular Inhomogeneities in the Course of Glassy Densification of Polyalcohols