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 nu cleation temperature TH = 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, TL ? 225 K, where the confined water shows a fragile-to-strong dynamic cross-over phe nomenon [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 [Poole, P. H., Sciortino, F., Essmann, U., Stanley, H. E. (1992) Nature 360:324-328].

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

MALLAMACE, Francesco;CORSARO, CARMELO;MAJOLINO, Domenico;VENUTI, Valentina;
2007-01-01

Abstract

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 nu cleation temperature TH = 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, TL ? 225 K, where the confined water shows a fragile-to-strong dynamic cross-over phe nomenon [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 [Poole, P. H., Sciortino, F., Essmann, U., Stanley, H. E. (1992) Nature 360:324-328].
2007
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11570/1704471
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