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Simulation studies of the atomic shear stress in the local potential energy minima (inherent structures) are reported for binary liquid mixtures in 2D and 3D. These inherent structure stresses are fundamental to slow stress relaxation and high viscosity in supercooled liquids. We find that the atomic shear stress in the inherent structures (IS) of both liquids at rest exhibits slowly decaying anisotropic correlations. We show that the stress correlations contributes significantly to the variance of the total shear stress of the IS configurations and consider the origins of the anisotropy and spatial extent of the stress correlations.

We demonstrate that irreversible structural reorganization is not necessary for the observation of yield behaviour in an amorphous solid. While the majority of solids strained to their yield point do indeed undergo an irreversible reorganization, we find a significant fraction of solids exhibit yield via a reversible strain. We also demonstrate that large instantaneous strains in excess of the yield stress can result in complete stress relaxation, a result of the large non-affine motions driven by the applied strain. The empirical similarity of the dependence of the ratio of stress over strain on the non-affine mean squared displacement with that for the shear modulus obtained from quiescent liquid at non-zero temperature supports the proposition that rigidity depends on the size of the sampled configurational space only, and is insensitive as to how this space is sampled.

We show that the long time tail of the shear stress autocorrelation, whose growth at large supercooling is responsible for the apparent divergence of the shear viscosity, is a direct result of a residual shear stress in the structures associated with the local potential minima. We argue that the essential mechanical transition experienced by a liquid on cooling occurs at a temperature well above the glass transition temperature and corresponds to the crossover from the high temperature liquid to the viscous liquid, the latter characterised by stress relaxation dominated by the residual stress. Following on from this observation, as the density is decreased, the local potential minima become unable to sustain any persistent stress (and, hence, support a glass transition), in a manner that can be explicitly connected to the interactions between atoms. The reported crossover implies an associated change in the mechanism of dissipation in liquids and, hence, raises the prospect of a coherent microscopic treatment of nonlinear rheology and the relationship between self diffusion and viscosity in supercooled liquids.

Vibrational density of states (VDOS) in a supercooled polydisperse liquid is computed by diagonalizing the Hessian matrix evaluated at the potential energy minima for systems with different values of polydispersity. An increase of polydispersity leads to an increase in relative population of the localized high-frequency modes. At low frequencies, the density of states show an excess compared to the Debye squared-frequency law, which has been identified with the boson peak. The height of the boson peak increases with polydispersity. The values of the participation ratio as well as the level spacing statistics demonstrate that the modes comprising the boson peak are largely delocalized. Interestingly, the intensity of the boson peak shows a rather narrow sensitivity to changes in temperature and is seen to persist even at high temperatures. Study of the difference spectrum at two different polydispersity reveals that the increase in the height of boson peak is due to a population shift from modes with frequencies above the maximum in the VDOS to that below the maximum, indicating an increase in the fraction of the unstable modes in the system. The latter is further supported by the facilitation of the observed dynamics by polydispersity. Since the strength of the liquid increases with polydispersity, the present result provides an evidence that the intensity of boson peak correlates positively with the strength of the liquid, as observed earlier in many experimental systems.

The relationship between the microscopic arrangement of molecules in a supercooled liquid and its slow dynamics at low temperature near glass transition is studied by Molecular Dynamics (MD) simulations. A Lennard-Jones liquid with polydispersity in size and mass of constituent particles is chosen as the model system. Our studies reveal that the local structure (that varies with polydispersity) plays a crucial role both in the slowing down of dynamics and in the growth of the dynamic heterogeneities, besides determining the glass forming ability (GFA) of the system. Increasing polydispersity at fixed volume fraction is found to suppress the rate of growth of dynamic correlations, as detected by the growth in the peak of the non-linear density response function. The growth in dynamical correlation is manifested in a stronger than usual breakdown of Stokes-Einstein relation at lower polydispersity at low temperatures and also leads to a decrease in the fragility of the system with polydispersity. We show that the suppression of the rate of growth of the dynamic heterogeneity can be attributed to the loss of structural correlations (as measured by the structure factor and the local bond orientational order) with polydispersity. While a critical polydispersity is required to avoid crystallization, we find that further increase in polydispersity lowers the glass forming ability (GFA).

Polydispersity is found to have a significant effect on the potential energy landscape; the the average inherent structure energy with temperature decreases with polydispersity. Increasing polydispersity at fixed volume fraction decreases the glass transition temperature and the fragility of glass formation analogous to the antiplasticization seen in some polymeric melts. An interesting temperature dependent crossover of heterogeneity with polydispersity is observed at low temperature due to the faster build-up of dynamic heterogeneity at lower polydispersity., Comment: 17 pages, 4 figures (Submitted to Phys. Rev. Lett.)