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When water freezes it sets up a crystal structure which aligns the hydrogen atoms of one molecule with the lone electron pairs on nearby oxygen atoms in other molecules. This arrangement as an optimal distance which determines the density of ice. This packing structure has an 'energy balance' associated with it that is a compromise between the attraction and repulsion of all involved atoms and their configurations with the water molecule.

When heat is added to ice the energy of the thermal vibrations of the individual molecules exceeds the repulsion energy between molecules but not their attractive energy. As I said before the packing structure is a balance of many factors and not all these factors have the same energy threshold. Therefore when ice melts it is easier for water to contract (become denser) then it is for it to expand. Once the temperature exceeds 4'C however the thermal energy exceeds all inter-molecular forces and 'ordinary' thermal expansion occurs.

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