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

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 spatiotemporal correlation among temperature fluctuations and examined the frequency dependent specific heat. The latter shows a rapid growth in the low frequency regime as temperature is cooled below 270 K. In order to understand the microscopic basis of this increase, we have performed a shell wise decomposition of contributions of distant molecules to the temperature fluctuations in a central molecule. This decomposition reveals the emergence, at low temperatures, of temporally slow, spatially long ranged large temperature fluctuations. The temperature fluctuation time correlation function (TFCF) can be fitted to a William-Watts stretched exponential form with the stretching parameter close to 0.6 at low temperatures, indicating highly non-exponential relaxation. Temperature dependence of the relaxation time of the correlation function can be fitted to Vogel-Fulcher-Tamermann expression which provides a quantitative measure of the fragility of the liquid. Interestingly, we find that the rapid growth in the relaxation time of TFCF with lowering temperature undergoes a sharp crossover from a markedly fragile state to a weakly fragile state around 220 K.Comment: 19 pages, 6 figures (including 1 supplemental figure

Multiple time scales hidden in heterogeneous dynamics of glass-forming liquids

A multi-time probing of density fluctuations is introduced to investigate hidden time scales of heterogeneous dynamics in glass-forming liquids. Molecular dynamics simulations for simple glass-forming liquids are performed, and a three-time correlation function is numerically calculated for general time intervals. It is demonstrated that the three-time correlation function is sensitive to the heterogeneous dynamics and that it reveals couplings of correlated motions over a wide range of time scales. Furthermore, the time scale of the heterogeneous dynamics $\tau_{\rm hetero}$ is determined by the change in the second time interval in the three-time correlation function. The present results show that the time scale of the heterogeneous dynamics $\tau_{\rm hetero}$ becomes larger than the $\alpha$-relaxation time at low temperatures and large wavelengths. We also find a dynamical scaling relation between the time scale $\tau_{\rm hetero}$ and the length scale $\xi$ of dynamical heterogeneity as $\tau_{\rm hetero} \sim \xi^{z}$ with $z=3$.Comment: 4 pages, 5 figures, to appear in Phys. Rev. E (Rapid Communications

Exploration of vitrification of water and Kauzmann entropy through complex specific heat: A journey through 'No Man's Land'

Frequency dependent specific heat, introduced by Grest and Nagel, offers valuable insight into the vitrification of supercooled liquid. We calculate this quantity and other thermodynamic properties of supercooled liquid water by varying temperature and density across the "no man's land" all the way to the formation of amorphous ice. The calculations are aided by very long computer simulations, often more than 50 $\mu s$ long. Density fluctuations that arise from the proximity to a putative liquid-liquid (LL) transition at 228 K, cast a long shadow on the properties of water, both above and below the LL transition. We carry out the calculation of the quantum mechanical static and frequency-dependent specific heats by combining seminal works by Lebowitz, Percus, and Verlet and Grest and Nagel with the harmonic approximation for the density of states. The obtained values are in quantitative agreement with all available experimental and numerical results of specific heats for both supercooled water and ice. We calculate the entropy at all the state points by integrating the specific heat. We find that the quantum corrected-contributions of intermolecular vibrational entropy dominate the excess entropy of amorphous phases over the crystal over a wide range of temperature. Interestingly, the vibrational entropy lowers the Kauzmann temperature, $T_{\rm K}$, to 130 K, just below the experimental glass-to-liquid water transition temperature, $T_{\rm g}$, of 136 K and the calculated $T_{\rm g}$ of 135 K in our previous study. A straightforward extrapolation of high temperature entropy from 250 K to below however would give a much higher value of $T_{\rm K}$ $\sim$ 190 K. The calculation of Lindemann ratios places the melting of amorphous ice $\sim$ 135 K. The amorphous state exhibits an extremely short correlation length for the distance dependence of orientational correlation.Comment: 34 pages, 10 figure

Electrical spin injection in p-type Si using Fe/MgO contacts

We report the successful electrical creation of spin polarization in p-type Si at room temperature by using an epitaxial MgO(001) tunnel barrier and Fe(001) electrode. Reflection high-energy electron diffraction observations revealed that epitaxial Fe/MgO(001) tunnel contacts can be grown on a (2 x 1) reconstructed Si surface whereas tunnel contacts grown on the (1 x 1) Si surface were polycrystalline. Transmission electron microscopy images showed a more flat interface for the epitaxial Fe/MgO/Si compared to that of the polycrystalline structure. For the Fe/MgO/p-Si devices, the Hanle and inverted Hanle effects were clearly observed at 300 K by using a three-terminal configuration, proving that spin polarization can be induced in the Si at room temperature. Effective spin lifetimes deduced from the width of the Hanle curve were 95 +/- 6 ps and 143 +/- 10 ps for the samples with polycrystalline and epitaxial MgO tunnel contacts, respectively. The observed difference can be qualitatively explained by the local magnetic field induced by the larger roughness of the interface of the polycrystalline sample. The sample with epitaxial Fe/MgO tunnel contact showed higher magnitude of the spin accumulation with a nearly symmetric behavior with respect to the bias polarity whereas that of the polycrystalline MgO sample exhibited a quite asymmetric evolution. This might be attributed to the higher degree of spin polarization of the epitaxial Fe/MgO(001) tunnel contact, which acts as a spin filter. Our experimental results suggest that an epitaxial MgO barrier is beneficial for creating spins in Si.Comment: Paper presented at SPIE Nanoscience + Engineering, Spintronics V session in San Diego, US on August 13th, 201