We perform molecular dynamics simulations to study the structure and dynamics of liquid water in neutral nanopores, which are generated by pinning a suitable subset of water molecules in an equilibrium configuration of a bulk system. It is found that such neutral confinement does not disturb the structure of water, in particular, the local tetrahedral order, while it imposes a pronounced spatial inhomogeneity on the dynamics of water. Specifically, when the pore wall is approached, hopping motion sets in and water dynamics slows down. We show that the logarithm of the correlation time is an exponential function of the distance to the wall, indicating a tremendous gradient of water mobility across the confinement. Upon cooling, the length scale associated with this exponential distance dependence and, thus, the range of the wall effect increases, at least down to the critical temperature of mode coupling theory, T(c). Also, the temperature dependence of water dynamics varies across the pore, i.e., fragility is high in the pore center, while it is low near the pore wall. Due to all these effects, time-temperature superposition is violated. Our observations for a neutral confinement reveal that specific interactions at hydrophilic or hydrophobic walls are not the main cause of spatially inhomogeneous dynamics of confined water. In view of similarities with the behavior of Lennard-Jones liquids in neutral confinements, one may rather speculate that the effects observed for confined water are general and result from the existence of a static contribution to the energy landscape, which is imprinted by an immobile environment.
We perform molecular dynamics simulations to study static and dynamic length scales in molecular supercooled liquids, in particular, water. For a determination of these scales, we use equilibrium configurations and pin appropriate subsets of molecules so as to obtain random matrices, cylindrical pores, and slit confinements. Static length scales ξ(s) are determined by analyzing overlap correlation functions for various fractions of pinned molecules or distances to the confining walls. For water in all confinements and for propylene oxide trimers in random geometry, a linear increase of ξ(s) with inverse temperature is found. Dynamic length scales ξ(d) are determined by analogous analysis of fraction-dependent or position-resolved correlation times of structural relaxation. While ξ(d) continuously grows upon cooling in the cylindrical and slit confinements, we find no evidence for a temperature dependence in random matrices, implying that molecular dynamics in parsed volumes is qualitatively different from that in bulk liquids. Finally, we study possible connections between the growth of the static and dynamic length scales and the slowdown of the structural relaxation of the supercooled bulk liquids. For water, we observe a linear relation between ln τ(α) and ξ(s)²/T in the whole accessible range down to the critical temperature of mode-coupling theory, T(c). In the weakly supercooled regime, the same relation holds also for ξ(d), as obtained from cylindrical and slit confinements, but deviations from this behavior are observed near T(c). The results are discussed in connection with random first-order theory and experimental studies of liquid dynamics in nanoscopic confinements and binary mixtures.
Aqueous systems are omnipresent in nature and technology. They show complex behaviors, which often originate in the existence of hydrogen-bond networks. Prominent examples are the anomalies of water and the non-ideal behaviors of aqueous solutions. The phenomenology becomes even richer when aqueous liquids are subject to confinement. To this day, many properties of water and its mixtures, in particular, under confinement, are not understood. In recent years, molecular dynamics simulations developed into a powerful tool to improve our knowledge in this field. Here, our simulation results for water and aqueous mixtures in the bulk and in various confinements are reviewed and some new simulation data are added to improve our knowledge about the role of interfaces. Moreover, findings for water are compared with results for silica, exploiting that both systems form tetrahedral networks.
We use molecular dynamics simulations to study anomalous internal protein dynamics observed for the backbone atoms of hydrated elastin and hydrated myoglobin in the picoseconds and nanoseconds regimes. The anomalous dynamics manifests itself in a sublinear increase of the atomic mean square displacements and in a power-law or logarithmic-like decay of correlation functions. We find that several, but not all, observations can be described in the frameworks of rugged potential-energy landscape and fractional Fokker-Planck approaches, in particular, a fractional Ornstein-Uhlenbeck process. Furthermore, mode-coupling theory allows us to rationalize findings at ambient temperatures, but there are deviations between theoretical predictions and simulation results related to the anomalous dynamics at cryogenic temperatures. We argue that the observations are consistent with a scenario where a broad β-relaxation peak shifts through the picoseconds and nanoseconds regimes when cooling from 300 to 200 K, say. Inspection of trajectories of consecutive nitrogen atoms along the protein backbone reveals that correlated forward-backward jumps, which exhibit a substantial degree of cooperativity, are a key feature of the anomalous dynamics.
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