Evidence of the existence of the low-density liquid phase in supercooled, confined water

Francesco Mallamace, Matteo Broccio, Carmelo Corsaro, Antonio Faraone, Domenico Majolino, Valentine Venuti, Li Liu, Chung Yuan Mou, Sow Hsin Chen

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265 Citations (Scopus)


By confining water in a nanoporous structure so narrow that the liquid could not freeze, it is possible to study properties of this previously undescribed system well below its homogeneous nucleation temperature T H = 231 K. Using this trick, we were able to study, by means of a Fourier transform infrared spectroscopy, vibrational spectra (HOH bending and OH-stretching modes) of deeply supercooled water in the temperature range 183 < T < 273 K. We observed, upon decreasing temperature, the building up of a new population of hydrogen-bonded oscillators centered around 3,120 cm -1, the contribution of which progressively dominates the spectra as one enters into the deeply supercooled regime. We determined that the fractional weight of this spectral component reaches 50% just at the temperature, T L ≈ 225 K, where the confined water shows a fragile-to-strong dynamic cross-over phenomenon [Ito, K., Moynihan, C. T., Angell, C. A. (1999) Nature 398:492-494]. Furthermore, the fact that the corresponding OH stretching spectral peak position of the low-density-amorphous solid water occurs exactly at 3,120 cm-1 [Sivakumar, T. C., Rice, S. A., Sceats, M. G. (1978) J. Chem. Phys. 69:3468-3476.] strongly suggests that these oscillators originate from existence of the low-density-liquid phase derived from the occurrence of the first-order liquid-liquid (LL) phase transition and the associated LL critical point in supercooled water proposed earlier by a computer molecular dynamics simulation.

Original languageEnglish
Pages (from-to)424-428
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number2
Publication statusPublished - Jan 9 2007
Externally publishedYes


  • Dynamic cross-over in water
  • Dynamic transitions in water
  • Fourier transform infrared spectroscopy
  • Low-density liquid water
  • Widom line in water

ASJC Scopus subject areas

  • General


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