qq-independent slow-dynamics in atomic and molecular systems

Investigating million-atom systems for very long simulation times, we demonstrate that the collective density-density correlation time ($\tau_{\alpha}$) in simulated supercooled water and silica becomes wavevector independent ($q^0$) when the probing wavelength is several times larger than the interparticle distance. The $q$-independence of the collective density-density correlation functions, a feature clearly observed in light-scattering studies of some soft-matter systems, is thus a genuine feature of many (but not all) slow-dynamics systems, either atomic, molecular or colloidal. Indeed, we show that when the dynamics of the density fluctuations is due to particle-type diffusion, as in the case of the Lennard Jones binary mixture model, the $q^0$ regime does not set in and the relaxation time continues to scale as $\tau_{\alpha} \sim q^{-2}$ even at small $q$.Comment: Includes the supplementary materia

Size dependence of dynamic fluctuations in liquid and supercooled water

We study the evolution of dynamic fluctuations averaged over different space lengths and time scales to characterize spatially and temporally heterogeneous behavior of TIP4P/2005 water in liquid and supercooled states. Analyzing a 250 000 molecules simulated system, we provide evidence of the existence, upon supercooling, of a significant enhancement of spatially localized dynamic fluctuations stemming from regions of correlated mobile molecules. We show that both the magnitude of the departure from the value expected for the system-size dependence of an uncorrelated system and the system size at which such a trivial regime is finally recovered clearly increase upon supercooling. This provides a means to estimate an upper limit to the maximum length scale of influence of the regions of correlated mobile molecules. Notably, such an upper limit grows two orders of magnitude on cooling, reaching a value corresponding to a few thousand molecules at the lowest investigated temperature.Fil: Montes de Oca, Joan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Accordino, Sebastián R.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Appignanesi, Gustavo Adrian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Handle, Philip H.. Universidad de Innsbruck; AustriaFil: Sciortino, Francesco. Università degli studi di Roma "La Sapienza"; Itali

Glass Polymorphism in TIP4P/2005 Water: A Description Based on the Potential Energy Landscape Formalism

The potential energy landscape (PEL) formalism is a statistical mechanical approach to describe supercooled liquids and glasses. Here we use the PEL formalism to study the pressure-induced transformations between low-density amorphous ice (LDA) and high-density amorphous ice (HDA) using computer simulations of the TIP4P/2005 molecular model of water. We find that the properties of the PEL sampled by the system during the LDA-HDA transformation exhibit anomalous behavior. In particular, at conditions where the change in density during the LDA-HDA transformation is approximately discontinuous, reminiscent of a first-order phase transition, we find that (i) the inherent structure (IS) energy, $e_\text{IS}(V)$, is a concave function of the volume, and (ii) the IS pressure, $P_\text{IS}(V)$, exhibits a van der Waals-like loop. In addition, the curvature of the PEL at the IS is anomalous, a non-monotonic function of $V$. In agreement with previous studies, our work suggests that conditions (i) and (ii) are necessary (but not sufficient) signatures of the PEL for the LDA-HDA transformation to be reminiscent of a first-order phase transition. We also find that one can identify two different regions of the PEL, one associated to LDA and another to HDA. Our computer simulations are performed using a wide range of compression/decompression and cooling rates. In particular, our slowest cooling rate (0.01 K/ns) is within the experimental rates employed in hyperquenching experiments to produce LDA. Interestingly, the LDA-HDA transformation pressure that we obtain at $T=80$ K and at different rates extrapolates remarkably well to the corresponding experimental pressure.Comment: Manuscript and Supplementary Materia

Condensation and Demixing in Solutions of DNA Nanostars and Their Mixtures

We present a numerical/theoretical approach to efficiently evaluate the phase diagram of self-assembling DNA nanostars. Combining input information based on a realistic coarse-grained DNA potential with the Wertheim association theory, we derive a parameter-free thermodynamic description of these systems. We apply this method to investigate the phase behavior of single components and mixtures of DNA nanostars with different numbers of sticky arms, elucidating the role of the system functionality and of salt concentration. Specifically, we evaluate the propensity to demix, the gas–liquid phase boundaries and the location of the critical points. The predicted critical parameters compare very well with existing experimental results for the available compositions. The approach developed here is very general, easily extensible to other all-DNA systems, and provides guidance for future experiments