Relaxation processes in supercooled confined water and implications for protein dynamics

We show that the viscosity-related main (alpha) relaxation of confined water vanishes at a temperature where the volume required for the cooperative alpha relaxation becomes larger than the size of the geometrically confined water cluster. This occurs typically around 200 K, implying that above this temperature we observe a merged alpha-beta relaxation, whereas below it only a local (beta) relaxation remains. This also means that such confined supercooled water does not exhibit any true glass transition, in contrast to other liquids in similar confinements. Furthermore, it implies that deeply supercooled water in biological systems, such as membranes and proteins, generally shows only a local beta relaxation, a finding of importance for low temperature properties of biological materials.     

Molecular dynamics simulation of ice nanocluster in supercooled water

The properties of the interface between an ice nanocluster and the surrounding water shell were investigated by the molecular simulation method for the SPC/E model in the temperature interval from 200 to 230?K. The melting point of the ice core was determined on the basis of the caloric curve and the behaviour of the diffusion coefficient. The change of the local structure was described by the orientational distribution functions and by the radial profiles of the local density, energy, and normal pressure.     

A molecular dynamics investigation of dynamical heterogeneity in supercooled water

We investigate the presence of dynamical heterogeneity in supercooled water with molecular dynamics simulations using the new water model proposed by Mahoney and Jorgensen [M.W. Mahoney, W.L. Jorgensen J. Chem. Phys. 112, 8910 (2000)]. Prompted by recent theoretical results [J.P. Garrahan, D. Chandler, Phys. Rev. Lett. 89, 35704 (2002)] we study the dynamical aggregation of the least and the most mobile molecules. We find dynamical heterogeneity in supercooled water and string-like dynamics for the most mobile molecules. We also find the dynamical aggregation of the least mobile molecules. The two kinds of dynamical aggregation appear however to be very different. Characteristic times are different and evolve differently. String-like motions appear only for the most mobile molecules, a result predicted by the facilitation theory. The aggregation of the least mobile molecules is more organized than the bulk while the opposite is observed for the most mobile molecules.     

Evidence of a two-state picture for supercooled water and its connections with glassy dynamics

The picture of liquid water as consisting of a mixture of molecules of two different structural states (structured, low-density molecules and unstructured, high-density ones) represents a belief that has been around for long time awaiting for a conclusive validation. While in the last years some indicators have indeed provided certain evidence for the existence of structurally different “species”, a more definite bimodality in the distribution function of a sound structural quantity would be desired. In this context, our present work combines the use of a structural parameter with a minimization technique to yield neat bimodal distributions in a temperature range within the supercooled liquid regime, thus clearly revealing the presence of two populations of differently structured water molecules. Furthermore, we elucidate the role of the inter-conversion between the identified two kinds of states for the dynamics of structural relaxation, thus linking structural information to dynamics, a long-standing issue in glassy physics.     

Viscosity and stress autocorrelation function in supercooled water: a molecular dynamics study

Following Guo, G.-J., and Zhang, Y.-G., 2001, Molec. Phys., 99, 283, which calculates the bulk and shear viscosities of SPC/E water at 30°C and 0.999 g cm^?3, further molecular dynamics simulations have been performed at state points of 0°C, ?20°C, ?40°C, and ?60°C along an approximate isobar with the previous state point. SACF and BACF (stress autocorrelation functions related to shear and bulk viscosities, respectively) of high precision have been obtained and compared for their similarities and differences. Shear and bulk viscosities calculated from them showed an increased deviation from real water with decreasing temperature. These correlation functions were then fitted using a uniform two-step relaxation function including a fast oscillatory Kohlrausch law and a slow straightforward Kohlrausch law. The fitting parameters of SACF and BACF have been analysed in detail, and several interesting dynamic phenomena were observed. (1) The oscillation frequency of SACF (44 ~ 48ps^?1) for short time intervals agrees with the stretching mode of hydrogen bonds, while that of BACF (7 ~ 12ps^?1) agrees with the bending mode of hydrogen bonds. (2) With decreasing temperature, the slow relaxation fraction of the BACF increases, while that of the SACF remains constant. (3) The exponents β in the Kohlrausch laws with values greater than 1 are obtained for BACF at ambient temperatures. (4) With regard to both shear and bulk viscosities, the slow relaxation time largely increases with decreasing temperature, while the fast relaxation time slightly decreases. These phenomena are qualitatively explained and discussed.     

Recent experimental aspects of the structure and dynamics of liquid and supercooled water

Liquid water, the most familiar liquid, is still not completely understood, even less so all the processes in which it participates. The directionality of the bonds and quantum aspects make the establishment of a complete theory difficult, particularly in the case of effective potentials built with spherical electrostatic forces. Recent work has focused on the hydrogen bonds formed between water molecules or with hydrophilic substrates. We describe the present situation of research concerning the so-called anomalies of liquid water at low temperature. Although without direct applications, this problem is consistently an object of discussion, enhanced by results from molecular dynamics simulations. Conversely, because in many situations where water plays a major role, such as, for example, in biology, only a few molecules are involved, the study of confined water is extremely important, sometimes decoupled from the more fundamental studies of bulk water. A short, but far from exclusive, summary of some of the more active domains of research concerning liquid water is given, mainly concerning interactions with other media.     

Optical Kerr effect in supercooled water

We present molecular dynamics simulations of the optical Kerr effect in liquid and supercooled water and compare with recent time-resolved Kerr spectroscopy measurements [R. Torre, Nature (London) 428, 296 (2004)]. The short time features of the Kerr response, characterized by peaks near 15, 60, and 160 fs, are weakly temperature dependent. The long-time decay is well described by a stretched exponential with a nearly constant stretch parameter and relaxation times that follow a power law approximately (T-T(S))(-gamma), with T(S)=198.3 K and gamma=2.35. Our findings are discussed in the light of the spectroscopy data and previous simulation analyzes of the structural relaxation in supercooled water.     

Intermediate range order in supercooled water

ABSTRACT

The temperature dependence of the heights of the first and second x-ray diffraction peaks in supercooled water measured down to 244?K are found to display very different behaviours. While the first peak intensity remains essentially constant, the second peak increases strongly with decreasing temperature. In real space this is concomitant with the reduction of the number of non-bonded interstitial molecules between the first and second shells. It is found that although the first O-O shell in supercooled water is unchanged upon supercooling, the variations in intermediate range order are mainly associated with the growth of a predominantly tetrahedral network that is distinctly different from ice-Ih. Moreover, in this temperature regime we find a direct correlation between the height of the second diffraction peak and the intensity changes in the 2nd, 3rd, 4th and 5th peaks in the oxygen-oxygen pair distribution function.     

Rotational dynamics of Di-tert-butyl-nitroxide in normal and supercooled water: an electron paramagnetic resonance study

In order to obtain dynamical information on the water solvent, which is characterized by a strong anomalous behavior in its structural and transport properties especially in the supercooled region, low concentration di-tert-butyl-nitroxide (DTBN) aqueous solutions were studied by Electron Paramagnetic Resonance spectroscopy in the temperature range from 28 down to ?17°C. The accurate spectra reconstruction, achieved by a multi-parameters Monte Carlo fitting algorithm, allowed us to reliably extract some relevant spectral parameters of the spin probe, which were connected to the probe dynamics in the framework of the motional narrowing magnetic relaxation theory. The observed trend with the temperature showed however a significant deviation from what expected from the magnetic relaxation model. This anomalous behavior is discussed in terms of the influence upon the probe motion of solvent-induced local fluctuating structures which, very likely, are connected to the water hydrogen bond network dynamics.     

X-ray analysis of supercooled water

X-ray diffraction patterns of supercooled water were obtained at -5 and -10°C. Pretreated X-ray film was used for the measurements. X-ray intensity was measured by counting the density of developed Ag grains under a microscope. The radial distribution functions were derived from the intensity curves.     

Anomalous scattering in supercooled ST2 water

ABSTRACT

Large-scale molecular dynamics (MD) simulations of systems containing up to 256,000 molecules were performed to investigate the scattering behaviour of the ST2 water model at deeply supercooled conditions. The simulations reveal that ST2 exhibits anomalous scattering, reminiscent of that observed in experiment, which is characterised by an increase in the static structure factor at low wavenumbers. This unusual behaviour in ST2 is linked with coupled fluctuations in density and local tetrahedral order in the liquid. The Ornstein–Zernike correlation length estimated from the anomalous scattering component exhibits power-law growth upon cooling, consistent with the existence of a liquid–liquid critical point (LLCP) in the ST2 model at ca. 245 K. Further, spontaneous liquid–liquid phase separation is observed upon thermally quenching a large system with 256,000 water molecules below the predicted critical temperature into the two-phase region. The large-scale MD simulations therefore confirm the existence of a metastable liquid–liquid phase transition in ST2 and support findings from previous computational studies performed using smaller systems containing only a few hundred molecules. We anticipate that our analysis may prove useful in interpreting recent scattering experiments that have been performed to search for an LLCP in deeply supercooled water.     

Nonlinear dynamics in sliding processes： the single-particle case

Dynamical behaviours of the motion of particles in a periodic potential under a constant driving velocity by a spring at one end are explored. In the stationary case, the stable equilibrium position of the particle experiences an elasticity instability transition. When the driving velocity is nonzero, depending on the elasticity coefficient and the pulling velocity, the system exhibits complicated and interesting dynamics, such as periodic and chaotic motions. The results obtained here may shed light on studies of dynamical processes in sliding friction.     

Local structural order and single-particle dynamics in metallic glass

The atomic dynamics of the amorphous metallic alloy Al₅₀Cu₅₀ is investigated in this work. The critical glass-forming temperature is defined from the behavior change of the Wendt—Abraham parameter and the pair-correlation entropy, and is T _c ≈ 500 K. It is shown that the power-fractional memory function allows us to describe in the framework of the mode-coupling theory the time dependences of the incoherent scattering functions obtained from the atomic dynamic simulations for the wide region of temperatures (T = 100–2000 K).     

Large decrease of fluctuations for supercooled water in hydrophobic nanoconfinement

Using Monte Carlo simulations, we study a coarse-grained model of a water layer confined in a fixed disordered matrix of hydrophobic nanoparticles at different particle concentrations c. For c=0, we find a first-order liquid-liquid phase transition (LLPT) ending in one critical point at low pressure P. For c>0, our simulations are consistent with a LLPT line ending in two critical points at low and high P. For c=25%, at high P and low temperature, we find a dramatic decrease of compressibility, thermal expansion coefficient, and specific heat. Surprisingly, the effect is present also for c as low as 2.4%. We conclude that even a small presence of hydrophobic nanoparticles can drastically suppress thermodynamic fluctuations, making the detection of the LLPT more difficult.     

Hydrophobic nanoconfinement suppresses fluctuations in supercooled water

We perform very efficient Monte Carlo simulations to study the phase diagram of a water monolayer confined in a fixed disordered matrix of hydrophobic nanoparticles between two hydrophobic plates. We consider different hydrophobic nanoparticle concentrations c. We adopt a coarse-grained model of water that, for c = 0, displays a first-order liquid-liquid phase transition (LLPT) line with negative slope in the pressure-temperature (P-T) plane, ending in a liquid-liquid critical point at about 174 K and 0.13 GPa. We show that upon increase of c the liquid-gas spinodal and the temperature of the maximum density line are shifted with respect to the c = 0 case. We also find dramatic changes in the region around the LLPT. In particular, we observe a substantial (more than 90%) decrease of isothermal compressibility, thermal expansion coefficient and constant-pressure specific heat upon increasing c, consistent with recent experiments. Moreover, we find that a hydrophobic nanoparticle concentration as small as c = 2.4% is enough to destroy the LLPT for P ≥ 0.16 GPa. The fluctuations of volume apparently diverge at P ≈ 0.16 GPa, suggesting that the LLPT line ends in an LL critical point at 0.16 GPa. Therefore, nanoconfinement reduces the range of P-T where the LLPT is observable. By increasing the hydrophobic nanoparticle concentration c, the LLPT becomes weaker and its P-T range smaller. The model allows us to explain these phenomena in terms of a proliferation of interfaces among domains with different local order, promoted by the hydrophobic effect of the water-hydrophobic-nanoparticle interfaces.