Supercooled confined water and the mode coupling crossover temperature

We present a molecular dynamics study of the single-particle dynamics of supercooled water confined in a silica pore. Two dynamical regimes are found. Close to the hydrophilic substrate molecules are below the mode coupling crossover temperature, T(C), already at ambient temperature. The water closer to the center of the pore (free water) approaches upon supercooling T(C) as predicted by mode coupling theories. For free water the crossover temperature and crossover exponent gamma are extracted from power-law fits to both the diffusion coefficient and the relaxation time of the late alpha region.     

The Boson peak interpretation and evolution in confined amorphous water

We study the evolution of the Boson peak for water confined in cement paste obtained by means of Inelastic Neutron Scattering from room temperature to the deep supercooled regime. We analyze the data in terms of a universal-like model, developed for glass forming liquids in the frame of the energy landscape. In such a way it is possible to discriminate between the fragile and strong glass forming character of supercooled liquids and the dynamical crossover, fragile to strong, between them. Hence, we confirm the link between the Boson peak and the water polymorphism. In particular, the main result is represented by a crossover from a local energetic minima configuration to that characteristic of saddle points on going towards the deep supercooled regime up to the dynamical arrest.     

Does confined water exhibit a fragile-to-strong transition?

The dynamics of supercooled confined water has recently been shown to have a pronounced, apparent fragile-to-strong transition (FST). Here we use broadband dielectric spectroscopy (10^-2–10⁹ Hz) to study the dynamics of water confined in silica matrices MCM-41 C10 and C18, with pore diameter of 21.4 and 36.1 ?, respectively. The local dynamics of water molecules and the dynamics of the hydroxyl groups on the inner wall of the pores are followed up to over 240 K. We argue that the reported FST for confined water is due to the vanishing of the cooperative α relaxation, which implies that it should not be interpreted as a true FST.     

Chain-length-dependent relaxation scenarios in an oligomeric glass-forming system: from merged to well-separated alpha and beta loss peaks

We have studied the relaxation dynamics of a homologous series of propylene glycol based dimethyl ethers in the supercooled regime by means of broadband dielectric spectroscopy. The system is chosen in order to minimize changes of the intermolecular interactions with varying molecular weight, M. A gradual transformation from a scenario of well-separated to one of merged alpha and beta loss peaks was observed with decreasing M. The results give strong evidence for the currently debated excess wing being due to an underlying beta relaxation. The study suggests that the main difference between glass formers with and without excess wings is the relaxation time at the merging temperature.     

Dynamics of supercooled confined water measured by deep inelastic neutron scattering

In this paper, we present the results of deep inelastic neutron scattering (DINS) measurements on supercooled water confined within the pores (average pore diameter ~ 20 Å) of a disordered hydrophilic silica matrix obtained through hydrolysis and polycondensation of the alkoxide precursor Tetra-Methyl-Ortho-Silicate via the sol-gel method. Experiments were performed at two temperatures (250 K and 210 K, i.e., before and after the putative liquid–liquid transition of supercooled confined water) on a “wet” sample with hydration h ~ 40% w/w, which is high enough to have water-filled pores but low enough to avoid water crystallization. A virtually “dry” sample at h ~ 7% was also investigated to measure the contribution of the silica matrix to the neutron scattering signal. As is well known, DINS measurements allow the determination of the mean kinetic energy and the momentum distribution of the hydrogen atoms in the system and therefore, allow researchers to probe the local structure of supercooled confined water. The main result obtained is that at 210 K the hydrogen mean kinetic energy is equal or even slightly higher than at 250 K. This is at odds with the predictions of a semiempirical harmonic model recently proposed to describe the temperature dependence of the kinetic energy of hydrogen in water. This is a new and very interesting result, which suggests that at 210 K, the water hydrogens experience a stiffer intermolecular potential than at 250 K. This is in agreement with the liquid–liquid transition hypothesis.     

非晶态物质原子局域连接度与弛豫动力学

非晶态物质的本质及形成过程是凝聚态物理领域最困难也是最有趣的问题之一.非晶形成过程在原子结构上不会衍生出人们在传统晶体结构里所熟悉的长程有序性,因此对于此类在自然界中广泛存在的物质形态,至今还没有有效的实验表征手段和理论研究方法.非晶态物质的原子结构及其构效关系的研究是凝聚态物理和材料科学等众多研究领域所关注的热点问题之一.随着对非晶态物质物性研究的深入,人们逐渐意识到非晶态物质中原子中程序对系统性质的重要影响,建立以中程序为基础的结构-动力学关系对于理解玻璃及玻璃转变的本质起着重要的作用.本文简要综述了基于图论提出的原子局域连接度这一新的结构序参量在液体和玻璃的结构及构效关系研究中的应用.新的结构序参量从过去侧重于关注局域原子团簇的种类和分布,转移到更加关注某一类具有特殊对称性的原子的空间连接情况,即更多地尝试从原子中程序的角度来建立非晶态物质中的构效关系.新的研究结果表明,局域连接度可与非晶态物质中原子的短时或长时动力学行为、输运方式、以及振动模态等一系列物理性质建立联系.     

Analysis of inelastic x-ray scattering spectra of low-temperature water

We analyze a set of high-resolution inelastic x-ray scattering (IXS) spectra from H2O measured at T=259, 273, and 294 K using two different phenomenological models. Model I, called the "dynamic cage model," combines the short time in-cage dynamics described by a generalized Enskog kinetic theory with a long-time cage relaxation dynamics described by an alpha relaxation. This model is appropriate for supercooled water where the cage effect is dominant and the existence of an alpha relaxation is evident from molecular-dynamics (MD) simulation data of extended simple point charge (SPC/E) model water. Model II is essentially a generalized hydrodynamic theory called the "three effective eigenmode theory" by de Schepper et al. 11. This model is appropriate for normal liquid water where the cage effect is less prominent and there is no evidence of the alpha relaxation from the MD data. We use the model I to analyze IXS data at T=259 K (supercooled water). We successfully extract the Debye-Waller factor, the cage relaxation time from the long-time dynamics, and the dispersion relation of high-frequency sound from the short time dynamics. We then use the model II to analyze IXS data at all three temperatures, from which we are able to extract the relaxation rate of the central mode and the damping of the sound mode as well as the dispersion relation for the high-frequency sound. It turns out that the dispersion relations extracted from the two models at their respective temperatures agree with each other giving the high-frequency sound speed of 2900+/-300 m/s. This is to be compared with a slightly higher value reported previously, 3200+/-320 m/s, by analyzing similar IXS data with a phenomenological-damped harmonic oscillator model 22. This latter model has traditionally been used exclusively for the analysis of inelastic scattering spectra of water. The k-dependent sound damping and central mode relaxation rate extracted from our model analyses are compared with the known values in the hydrodynamic limit.     

On the behaviour of supercooled liquids and polymers in nano-confinement

ABSTRACT

Size effects play an important role in structural phase transitions, melting transitions, in martensitic materials, glass transitions, etc. Very often the question arises, whether a measured size effect originates from the geometrical confinement itself, or if it appears due to the interaction with the limiting surface. Using dynamic mechanical analysis (DMA) technique we have studied various microphase segregated polymers, molecular glass forming liquids and supercooled water confined in nanoporous silica as well as in biological tissues. Here we show on some selected examples that DMA measurements can be used to study relaxation processes in detail and to disentangle in favourable cases pure pore size effects from effects that are induced by the confining surface.     

Model for single-particle dynamics in supercooled water

We analyze a set of 10 M-step molecular dynamics (MD) data of low-temperature SPC/E model water with a phenomenological analytical model. The motivation is twofold: to extract various k-dependent physical parameters associated with the single-particle or the self-intermediate scattering functions (SISFs) of water at a deeply supercooled temperature and to apply this analytical model to analyses of new high resolution quasielastic neutron scattering data presented elsewhere. The SISF of the center of mass computed from the MD data show clearly time-separated two-step relaxations with a well defined plateau in between. We model the short time relaxation of the test particle as a particle trapped in a harmonical potential well with the vibrational frequency distribution function having a two-peak structure known from previous inelastic neutron scattering experiments. For the long time part of the relaxation, we take the alpha relaxation suggested by mode-coupling theory. The model fits the low-temperature SISF over the entire time range from 1 fs to 10 ns, allowing us to extract peak positions of the vibrational density of states, the structural relaxation rate 1/tau of the cage (the potential well) and the stretch exponent beta. The structural relaxation rate has a power law dependence on the magnitude of the wave vector transfer k and the stretch exponent varies from 0.55 at large k to unity at small k.     

Transport properties of supercooled confined water

This article presents an overview of recent experiments performed on transport properties of water in the deeply supercooled region, a temperature region of fundamental importance in the science of water. We report data of nuclear magnetic resonance, quasi-elastic neutron scattering, Fourier-transform infrared spectroscopy, and Raman spectroscopy, studying water confined in nanometer-scale environments. When contained within small pores, water does not crystallise, and can be supercooled well below its homogeneous nucleation temperature T_h. On this basis it is possible to carry out a careful analysis of the well known thermodynamical anomalies of water. Studying the temperature and pressure dependencies of water dynamics, we show that the liquid-liquid phase transition (LLPT) hypothesis represents a reliable model for describing liquid water. In this model, water in the liquid state is a mixture of two different local structures, characterised by different densities, namely the low density liquid (LDL) and the high-density liquid (HDL). The LLPT line should terminate at a special transition point: a low-T liquid-liquid critical point. We discuss the following experimental findings on liquid water: (i) a crossover from non-Arrhenius behaviour at high T to Arrhenius behaviour at low T in transport parameters; (ii) a breakdown of the Stokes-Einstein relation; (iii) the existence of a Widom line, which is the locus of points corresponding to maximum correlation length in the p-T phase diagram and which ends in the liquid-liquid critical point; (iv) the direct observation of the LDL phase; (v) a minimum in the density at approximately 70 K below the temperature of the density maximum. In our opinion these results represent the experimental proofs of the validity of the LLPT hypothesis.     

Apparent finite-size effects in the dynamics of supercooled liquids

Molecular dynamics simulations are performed for a supercooled simple liquid with changing the system size from N=108 to 10(4) to examine possible finite-size effects. Although almost no systematic deviation is detected in the static pair correlation functions, it is demonstrated that the structural alpha relaxation in a small system becomes considerably slower than that in larger systems for temperatures below T(c) at which the size of the cooperative particle motions becomes comparable to the unit cell length of the small system. The discrepancy increases with decreasing temperature.     

Compressed-exponential relaxations in supercooled liquid trehalose

We investigated the α-relaxations in supercooled liquid trehalose by using photon correlation spectroscopy (PCS) and found an interesting compressed-exponential relaxation at temperatures above 140 °C. The q^?1 dependence of its relaxation time corresponds to an ultraslow ballistic motion due to the local structure rearrangements. In the same temperature range, we found the glycosidic bond structure changes in trehalose molecule from the Raman scattering and the X-ray direction measurements. We concluded that the compressed-exponential relaxation in supercooled liquid trehalose might originate from the intra-molecular (glycosidic bond) structure change.     

Dielectric investigation of the temperature dependence of the nonexponentiality of the dynamics of polymer melts

Using broad band dielectric spectroscopy (10(-5)-10(9) Hz), combining time domain and frequency domain techniques, we study the temperature dependence of the non-Debye character of the alpha relaxation of polymer melts in the glass transition temperature T(g) range. The alpha relaxation process is described in terms of the Kohlrausch-Williams-Watts relaxation function which has a single parameter beta to characterize the nonexponentiality of the relaxation. At high temperatures, beta remains nearly insensitive to temperature changes, whereas in the vicinity of T(g) a nearly linear increasing of beta with temperature is found. The temperature range where the change of the beta(T) behavior occurs is located for all the polymers investigated around 1.2T(g). Moreover, our results indicate a common value of beta approximately equal to 1/3 at the temperature where the relaxation time diverges. The beta(T) behavior near T(g) is discussed in terms of a "rugged landscape" phase space which allows us to rationalize both the beta(T) behavior observed as well as the similarities of our findings near T(g) with the results reported in simulations on Ising spin glasses and other model systems.     

The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the (P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the “low-density liquid” (LDL) and “high-density liquid” (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T_W as the (P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.     

Does the arrhenius temperature dependence of the Johari-Goldstein relaxation persist above T(g)?

Dielectric spectra of the polyalcohols sorbitol and xylitol were measured under isobaric pressures up to 1.8 GPa. At elevated pressure, the separation between the alpha and beta relaxation peaks is larger than at ambient pressure, enabling the beta relaxation times to be unambiguously determined. Taking advantage of this, we show that the Arrhenius temperature dependence of the beta relaxation time does not persist for temperatures above T(g). This result, consistent with inferences drawn from dielectric relaxation measurements at ambient pressure, is obtained directly, without the usual problematic deconvolution the beta and alpha processes.     

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.     

Microscopic theory of heterogeneity and nonexponential relaxations in supercooled liquids.

Recent experiments show that supercooled liquids around the glass transition temperature are "dynamically heterogeneous" [H. Sillescu, J. Non-Cryst. Solids 243, 81 (1999)]. Such heterogeneity is expected from the random first order transition theory of the glass transition. Using a microscopic approach based on this theory, we derive a relation between the departure from Debye relaxation as characterized by the beta value of a stretched exponential response function, phi(t) = e(-(t/tau(KWW))beta), and the fragility of the liquid. The beta value is also predicted to depend on temperature and to vanish as the ideal glass transition is approached at the Kauzmann temperature.     

Glass transition and relaxation processes in supercooled water

Many of water's peculiar physical properties are still not well understood, and one of the most important unresolved questions is its glass transition related dynamics. The consensus has been to accept a glass transition temperature (T(g)) around 136 K, but this value has been questioned and reassigned to about 165 K. We find evidence that the dielectric relaxation process of confined water that has been associated with the long accepted T(g) of water (130-140 K) must be a local process which is not related to the actual glass transition. Rather, our data indicate a glass transition at 160-165 K for bulk water and about 175 K for confined water (depending on the confining system).     

Anisotropic local stress and particle hopping in a deeply supercooled liquid

The origin of the microscopic motions that lead to stress relaxation in deeply supercooled liquid remains unclear. We show that in such a liquid the stress relaxation is locally anisotropic which can serve as the driving force for the hopping of the system on its free energy surface. However, not all hoppings are equally effective in relaxing the local stress, suggesting that diffusion can decouple from viscosity even at the local level. On the other hand, orientational relaxation is found to be always coupled to stress relaxation.