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We have thoroughly investigated the crystal structure of ice evolved from super cooled water confined in MCM-41 cylindrical nano pores through a synchrotron-based X-ray diffraction (XRD) technique for two different levels of pore filling. A rigorous analysis of XRD data shows that the nucleation dynamics and the structure of nucleated ice highly depend on the level of pore filling. In the nearly fully hydrated pores, ice crystallites start nucleating inside the pores below 240 K and creep out of the pores to form bulk crystals having crystalline structure of a mixed phase of hexagonal and cubic forms. In the partially hydrated pores, on the other hand, ice crystals cannot creep out of the pore crossing the energy barrier. The crystalline ice particles remaining inside the cylindrical pore show a short range "cubic rich" structure. The "pure cubic" phase has not been identified at either of the pore fillings in these 2.5 nm average size pores. A large fraction of water inside the pores remains in the super cooled liquid phase even at 180 K. This observation is relevant for understanding the ice nucleation through the pore condensation and freezing mechanism, which is a major pathway for the formation of cirrus clouds in the upper atmosphere.

Binary phase (BP) diagrams have been a cornerstone in both the industrial and the academic research. Traditionally, the two-component BP diagrams always consider a finite amount of solute in a finite solvent host. Here, we consider a special situation: a single solute molecule in a structurally different solvent host and pose the question “Can the traditional BP diagram account for the behavior of a single solute in a finite solvent host?” To date, this aspect remains unexplored because of both practical difficulties in probing such dilute solutions and conceptual difficulties in formulating a BP diagram for such a single solute molecule case. In this work, we have overcome the experimental barrier and produced such a system in ethanolic solutions of a neutral solute molecule by exploiting the ethanol’s property of crystallization from a translationally rigid plastic crystalline state. We studied the freezing behavior of dilute solutions of nitroxyl spin probes, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO)...

Liquid water (LW) existence in pure ice below 273 K has been a controversial aspect primarily because of the lack of experimental evidence. Recently, electron paramagnetic resonance (EPR) has been used to study deeply supercooled water in a rapidly frozen polycrystalline ice. The same technique can also be used to probe the presence of LW in polycrystalline ice that has formed through a more conventional, slow cooling one. In this context, the present study aims to emphasize that in case of an external probe involving techniques such as EPR, the results are influenced by the binary phase (BP) diagram of the probe-water system, which also predicts the existence of LW domains in ice, up to the eutectic point. Here we report the results of our such EPR spin-probe studies on water, which demonstrate that smaller the concentration of the probe stronger is the EPR evidence of liquid domains in polycrystalline ice. We used computer simulations based on stochastic Liouville theory to analyze the lineshapes of the EPR spectra. We show that the presence of the spin probe modifies the BP diagram of water, at very low concentrations of the spin probe. The spin probe thus acts, not like a passive reporter of the behavior of the solvent and its environment, but as an active impurity to influence the solvent. We show that there exists a lower critical concentration, below which BP diagram needs to be modified, by incorporating the effect of confinement of the spin probe. With this approach, we demonstrate that the observed EPR evidence of LW domains in ice can be accounted for by the modified BP diagram of the probe-water system. The present work highlights the importance of taking cognizance of the possibility of spin probes affecting the host systems, when interpreting the EPR (or any other probe based spectroscopic) results of phase transitions of host, as its ignorance may lead to serious misinterpretations.

The low temperature behavior of water and kinetics of ice nucleation in titania mesopores have been probed by positron annihilation lifetime spectroscopy as a function of pore filling. It is revealed that water undergoes complete freezing at around 220 K when more than 50% of the pore volume is filled and such freezing is hindered at lower hydration levels. A model describing progressive trapping of positronium by ice nuclei in liquid water during the phase transition is employed to estimate the energy associated with the nucleation under confinement. It is observed that the energy for ice nucleation in confinement is less than the activation energy for nucleation in bulk water because of the surface assisted nucleation inside the pore. Interestingly, energy for nucleation is seen to decrease with the lowering of hydration level and ascribed to the curtailed hydrogen bonding network of water at lower pore filling.