Chandan Dasgupta

Growing length and time scales in glass-forming liquids

The glass transition, whereby liquids transform into amorphous solids at low temperatures, is a subject of intense research despite decades of investigation. Explaining the enormous increase in relaxation times of a liquid upon supercooling is essential for understanding the glass transition. Although many theories, such as the Adam–Gibbs theory, have sought to relate growing relaxation times to length scales associated with spatial correlations in liquid structure or motion of molecules, the role of length scales in glassy dynamics is not well established. Recent studies of spatially correlated rearrangements of molecules leading to structural relaxation, termed “spatially heterogeneous dynamics,” provide fresh impetus in this direction. A powerful approach to extract length scales in critical phenomena is finite-size scaling, wherein a system is studied for sizes traversing the length scales of interest. We perform finite-size scaling for a realistic glass-former, using computer simulations, to evaluate the length scale associated with spatially heterogeneous dynamics, which grows as temperature decreases. However, relaxation times that also grow with decreasing temperature do not exhibit standard finite-size scaling with this length. We show that relaxation times are instead determined, for all studied system sizes and temperatures, by configurational entropy, in accordance with the Adam–Gibbs relation, but in disagreement with theoretical expectations based on spin-glass models that configurational entropy is not relevant at temperatures substantially above the critical temperature of mode-coupling theory. Our results provide new insights into the dynamics of glass-forming liquids and pose serious challenges to existing theoretical descriptions.

Is There a Growing Correlation Length near the Glass Transition

We present the results of a molecular-dynamics study on a Lennard-Jones mixture. Measurements of density and bond-angle correlation functions show that the answer to the question posed in the title is NO. We also show that icosahedral order plays no special role in the glass transition, but that a normalized measure of the persistence of orientational correlations in the glass shows a systematic dependence on the spherical harmonic index l.

Growth mechanism of nanocrystals in solution: ZnO, a case study.

We investigate the mechanism of growth of nanocrystals from solution using the case of ZnO. Spanning a wide range of values of the parameters, such as the temperature and the reactant concentration that control the growth, our results establish a qualitative departure from the widely accepted diffusion controlled coarsening (Ostwald ripening) process quantified in terms of the Lifshitz-Slyozov-Wagner theory. Further, we show that these experimental observations can be qualitatively and quantitatively understood within a growth mechanism that is intermediate between the two well-defined limits of diffusion control and kinetic control.

Thermodynamics of water entry in hydrophobic channels of carbon nanotubes

Experiments and computer simulations demonstrate that water spontaneously fills the hydrophobic cavity of a carbon nanotube. To gain a quantitative thermodynamic understanding of this phenomenon, we use the recently developed two phase thermodynamics method to compute translational and rotational entropies of confined water molecules inside single-walled carbon nanotubes and show that the increase in energy of a water molecule inside the nanotube is compensated by the gain in its rotational entropy. The confined water is in equilibrium with the bulk water and the Helmholtz free energy per water molecule of confined water is the same as that in the bulk within the accuracy of the simulation results. A comparison of translational and rotational spectra of water molecules confined in carbon nanotubes with that of bulk water shows significant shifts in the positions of the spectral peaks that are directly related to the tube radius.

Single-File Diffusion of Confined Water Inside SWNTs: An NMR Study

We report a nuclear magnetic resonance (NMR) study of confined water inside approximately 1.4 nm diameter single-walled carbon nanotubes (SWNTs). We show that the confined water does not freeze even up to 223 K. A pulse field gradient (PFG) NMR method is used to determine the mean squared displacement (MSD) of the water molecules inside the nanotubes at temperatures below 273 K, where the bulk water outside the nanotubes freezes and hence does not contribute to the proton NMR signal. We show that the mean squared displacement varies as the square root of time, predicted for single-file diffusion in a one-dimensional channel. We propose a qualitative understanding of our results based on available molecular dynamics simulations.

Breakdown of the Stokes-Einstein relation in two, three, and four dimensions

The breakdown of the Stokes-Einstein (SE) relation between diffusivity and viscosity at low temperatures is considered to be one of the hallmarks of glassy dynamics in liquids. Theoretical analyses relate this breakdown with the presence of heterogeneous dynamics, and by extension, with the fragility of glass formers. We perform an investigation of the breakdown of the SE relation in 2, 3, and 4 dimensions in order to understand these interrelations. Results from simulations of model glass formers show that the degree of the breakdown of the SE relation decreases with increasing spatial dimensionality. The breakdown itself can be rationalized via the difference between the activation free energies for diffusivity and viscosity (or relaxation times) in the Adam-Gibbs relation in three and four dimensions. The behavior in two dimensions also can be understood in terms of a generalized Adam-Gibbs relation that is observed in previous work. We calculate various measures of heterogeneity of dynamics and find that the degree of the SE breakdown and measures of heterogeneity of dynamics are generally well correlated but with some exceptions. The two-dimensional systems we study show deviations from the pattern of behavior of the three- and four-dimensional systems both at high and low temperatures. The fragility of the studied liquids is found to increase with spatial dimensionality, contrary to the expectation based on the association of fragility with heterogeneous dynamics.

Strongly anisotropic orientational relaxation of water molecules in narrow carbon nanotubes and nanorings.

Molecular dynamics simulations of the orientational dynamics of water molecules confined in narrow carbon nanotubes and nanorings reveal that confinement leads to strong anisotropy in the orientational relaxation. The relaxation of the aligned dipole moments, occurring on a time scale of nanoseconds, is 3 orders of magnitude slower than that of bulk water. In contrast, the relaxation of the vector joining the two hydrogens is ten times faster compared to bulk, with a time scale of about 150 fs. The slow dipolar relaxation is mediated by the hopping of orientational defects, which are nucleated by the water molecules outside the tube, across the linear water chain.

Jump reorientation of water molecules confined in narrow carbon nanotubes.

We used molecular dynamics (MD) simulations to study the reorientational dynamics of water molecules confined inside narrow carbon nanotubes immersed in a bath of water. Our simulations show that the confined water molecules exhibit bistability in their reorientational relaxation, which proceeds by angular jumps between the two stable states. The angular jump of a water molecule in the bulk involves the breaking of a hydrogen bond with one of its neighbors and the formation of a hydrogen bond with a different neighbor. In contrast, the angular jump of a confined water molecule corresponds to an interchange of the two hydrogen atoms that can form a hydrogen bond with the same neighbor. The free energy barrier between these two states is a few kBT. The analytic solution of a simplified two-state jump model that qualitatively explains the reorientational behavior observed in simulations is also presented.

Spatiotemporal Rheochaos in Nematic Hydrodynamics

Motivated by recent observations of rheochaos in sheared wormlike micelles, we study the coupled nonlinear partial differential equations for the hydrodynamic velocity and order-parameter fields in a sheared nematogenic fluid. In a suitable parameter range, we find irregular, dynamic shear banding and establish by decisive numerical tests that the chaos we observe in the model is spatiotemporal in nature.

Adam-Gibbs relation for glass-forming liquids in two, three, and four dimensions.

The Adam-Gibbs relation between relaxation times and the configurational entropy has been tested extensively for glass formers using experimental data and computer simulation results. Although the form of the relation contains no dependence on the spatial dimensionality in the original formulation, subsequent derivations of the Adam-Gibbs relation allow for such a possibility. We test the Adam-Gibbs relation in two, three, and four spatial dimensions using computer simulations of model glass formers. We find that the relation is valid in three and four dimensions. But in two dimensions, the relation does not hold, and interestingly, no single alternate relation describes the results for the different model systems we study.