Frequency dependence of specific heat in supercooled liquid water and emergence of correlated dynamics.

  title={Frequency dependence of specific heat in supercooled liquid water and emergence of correlated dynamics.},
  author={Shinji Saito and Iwao Ohmine and Biman Bagchi},
  journal={The Journal of chemical physics},
  volume={138 9},
Molecular origin of the well-known specific heat anomaly in supercooled liquid water is investigated here by using extensive computer simulations and theoretical analyses. A rather sharp increase in the values of isobaric specific heat with lowering temperature and the weak temperature dependence of isochoric specific heat in the same range are reproduced in simulations. We calculated the spatio-temporal correlation among temperature fluctuations and examined the frequency dependent specific… 

Figures, Tables, and Topics from this paper

Breakdown of the Stokes-Einstein relation in supercooled water: the jump-diffusion perspective.
A detailed and state-of-the-art analysis of the past and present works on the breakdown of the Stokes-Einstein relation (SER) in supercooled water with a specific focus on the new TJD approach for explaining the breakdown.
Thermodynamic picture of vitrification of water through complex specific heat and entropy: A journey through "no man's land".
It is found that the quantum corrected-contributions of intermolecular vibrational entropy dominate the excess entropy of amorphous phases over the crystal over a wide range of temperatures.
Fragile to strong crossover at the Widom line in supercooled aqueous solutions of NaCl.
The results show that the phenomenology of supercooled water transfers from bulk to solution where the study of thesupercooled region is experimentally less difficult.
Macro and nano scale modelling of water-water interactions at ambient and low temperature: relaxation and residence times.
It can be concluded that the distribution of times already reported for the dynamics of water surrounding proteins can not be exclusively due to the presence of the biomolecule itself since isolated water also exhibits such behaviour.
Tetrahedral structure of supercooled water at ambient pressure and its influence on dynamic relaxation: Comparative study of water models
Abstract In this paper, we investigated the tetrahedral structure of supercooled water at ambient pressure and its influence on dynamic relaxation by comparing simulation results of TIP4P/2005 and
Thermal Conductivity of Supercooled Water: An Equilibrium Molecular Dynamics Exploration.
  • N. English, J. Tse
  • Chemistry, Medicine
    The journal of physical chemistry letters
  • 2014
The thermal conductivity of both supercooled and ambient-temperature water at atmospheric pressure has been computed over the 140-270 K temperature range for three popular water models via
Crucial role of fragmented and isolated defects in persistent relaxation of deeply supercooled water.
It is found that structural and dynamical instabilities are hidden in the experimentally inaccessible region between 235 K and 150 K, and a hitherto undiscovered fragmentation from 220 K to 190 K is found, which is the breakup of large clusters consisting of molecules with a locally distorted tetrahedral structure into small pieces with one or two isolated defects.
Two-state thermodynamics and the possibility of a liquid-liquid phase transition in supercooled TIP4P/2005 water.
The results suggest the presence of a liquid-liquid critical point and are consistent with the existence of a LLPT in this model for the simulated length and time scales, and are compared with other popular water-like models, namely, mW and ST2, and with real water, all of which are well described by two-state thermodynamics.
Identifying time scales for violation/preservation of Stokes-Einstein relation in supercooled water
The temperature dependence of various time scales associated with structural relaxation, hydrogen bond breakage, stress relaxation, and dynamic heterogeneities can be definitely classified into only two classes and the mechanism of SE violation is attributed to the attained solidity upon supercooling, which is in accord with the growth of non-Gaussianity and spatially heterogeneous dynamics.
Correlation between thermodynamic anomalies and pathways of ice nucleation in supercooled water.
D density functional theoretical approach is employed to find nucleation free energy barrier in different regions of phase diagram and makes a number of striking predictions, such as a dramatic lowering of nucleation barrier due to presence of a metastable intermediate phase and crossover in the dependence of freeEnergy barrier on temperature near liquid-liquid critical point.


Growing correlation length in supercooled water.
This is the first direct estimation of the Widom line of supercooled water through the analysis of structural correlations, defined by the maximum isobaric expansivity, coincides with the maximum rate of change in the local structure of water.
The pronounced increases in isothermal compressibility, isobaric heat capacity, and in the magnitude of the thermal expansion coefficient of liquid water upon supercooling have been interpreted
Frequency dependent heat capacity within a kinetic model of glassy dynamics.
The relative amplitudes of the beta- and alpha-peaks in the present framework are found to depend on several characteristic features of the energy landscape, including the extent of cooperativity requirement for the alpha-relaxation and the asymmetry of the double well.
Isothermal compressibility of supercooled water and evidence for a thermodynamic singularity at −45°C
Using a capillary technique for small samples, the isothermal compressibility κ T of water has been measured to −26°C. Accelerating increases of κ T at the lower temperatures can be described by an
Evidence of the existence of the low-density liquid phase in supercooled, confined water
The observation of a new population of hydrogen-bonded oscillators centered around 3,120 cm−1 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.
The anomalous behavior of the density of water in the range 30 K < T < 373 K
From analyses of the profile of the OH stretching spectra, the fractional weight of the two main spectral components characterized by two different local hydrogen bond structures are determined, as predicted by the liquid–liquid phase transition hypothesis of liquid water, the low- and the high-density liquid phases.
Equation of state of supercooled water simulated using the extended simple point charge intermolecular potential
We carry out extensive molecular dynamics simulations in order to evaluate the thermodynamic equation of state of the extended simple point charge model of water (customarily described by the acronym
Simulation Study on the Diffusive Motion in Deeply Supercooled Water
The diffusion process in supercooled liquid water has been studied by a series of molecular dynamics simulations using systems of 216 ST2-model molecules in the temperature range between 255 and 360
Frequency-dependent specific heat of viscous silica
We apply the Mori-Zwanzig projection operator formalism to obtain an expression for the frequency dependent specific heat c(z) of a liquid. By using an exact transformation formula due to Lebowitz et
Line of compressibility maxima in the phase diagram of supercooled water
We evaluate thermodynamic, structural, and transport properties from extensive molecular-dynamics computer simulations of the ST2 and TIP4P models of liquid water over a wide range of thermodynamic