Water and solutions at negative pressure: Roman spectroscopic study to -80 megapascals

Microscopic inclusions of aqueous fluids trapped in interstices in quartz and other crystals provide novel systems for the deliberate study of liquids under tension. Liquids under tension should differ in interesting ways from those at ambient pressure or compressed liquids because attractive, rather than repulsive, forces should dominate their behavior. Static tensions in excess of 100 megapascals (∼1000 atmospheres) have been obtained reproducibly. Video-recorded observations of the final liquid rupture process, coupled with extrapolations of data at positive pressure, suggest that the homogeneous vapor nucleation point was reached in two of the cases studied. Raman spectra of the fluids at -80 megapascals show that an isothermal volume stretch of ∼5 percent by volume has only a weak effect on the spectral features and is similar to the effect of isobaric heating.