Heterodyne detected transient gratings in supercooled molecular liquids

We present an analysis, based on a phenomenological set of Generalised Navier-Stokes equations, of Heterodyne Detected Transient Gratings on supercooled molecular liquids of anisotropic molecules. This set of equations generalises equations proven in Franosch, Latz and Pick [24] for the same type of liquids. It also takes into account the three different sources generated by the laser pumping process pertinent for these experiments. We give analytical expressions for the response functions that can be measured using the different polarisation of the experimental set-up. Specialising to the case of parallel polarisation (where longitudinal phonons are launched), we show that each response function is a sum of the same seven elementary response functions (ERFs) whose time and temperature evolutions are individually analysed. We also show that the response functions corresponding to two of the sources can be directly connected to the Laplace Transform of a light scattering signal. The ERFs generated by the heat-absorption process, which is the third source, are of a different nature. They do not have the same time and temperature behaviours and they can provide, inter alia, unique information on the rotation-translation coupling function characteristic of these liquids.Received: 5 January 2004, Published online: 29 June 2004PACS: 64.70.Pf Glass transitions - 78.47. + p Time-resolved optical spectroscopies and other ultrafast optical measurements in condensed matter - 61.25.Em Molecular liquidsR. Gupta: Present address: Dept of Physics,1110 W Green St, Urbana, Ill 61801, USA.     

Light scattering by transverse waves in supercooled liquids and application to metatoluidine

We discuss the hydrodynamic equations which describe the shear dynamics of a liquid composed of anisotropic molecules, both in its normal and its supercooled phases. We use these equations to analyze 90 depolarized light scattering experiments performed in the supercooled phase of a glass forming liquid, metatoluidine, and show that the information extracted from this analysis is consistent with independent shear viscosity measurements performed on that liquid in the same temperature range. Received 28 April 1998     

Role of unstable directions in the equilibrium and aging dynamics of supercooled liquids

The connectivity of the potential energy landscape in supercooled atomic liquids is investigated through a calculation of the instantaneous normal modes spectrum and a detailed analysis of the unstable directions in configuration space. We confirm the hypothesis that the mode-coupling critical temperature is the T at which the dynamics crosses over from free to activated exploration of configuration space. We also observe changes in the local connectivity of configuration space sampled during aging, following a temperature jump from a liquid to a glassy state.     

Light scattering by longitudinal acoustic modes in molecular supercooled liquids I: phenomenological approach

We derive expressions for the intensity of the Brillouin polarized spectrum of a molecular liquid formed of axially symmetric molecules. These expressions take into account both the molecular dielectric anisotropy and the modulation of the local polarisability by density fluctuations. They also incorporate all the retardation effects which occur in such liquids. We show that the spectrum splits into a q-independent rotational contribution and q-dependent term, which reflects the propagation of longitudinal acoustic modes. In the latter, the two light scattering mechanisms enter on an equal footing and generate three scattering channels. We study the influence of the two new channels and show that they may substantially modify the Brillouin line-shape when the relaxation time of the supercooled liquid and the period of the acoustic excitation are of the same order of magnitude. Received 14 August 2002 Published online 4 February 2003 RID="a" ID="a"e-mail: franosch@hmi.de     

Algorithm for molecular dynamics simulations of spin liquids

A new symplectic time-reversible algorithm for numerical integration of the equations of motion in magnetic liquids is proposed. It is tested and applied to molecular dynamics simulations of a Heisenberg spin fluid. We show that the algorithm exactly conserves spin lengths and can be used with much larger time steps than those inherent in standard predictor-corrector schemes. The results obtained for time correlation functions demonstrate the evident dynamic interplay between the liquid and magnetic subsystems.     

Heterogeneities in supercooled liquids: a density-functional study

A metastable state, characterized by a low degree of mass localization, is identified using density-functional theory (DFT). This free energy minimum, located through the proper evaluation of competing terms in the free energy functional, is independent of the specific form of the DFT used. Computer simulation results on particle motion indicate that this heterogeneous state corresponds to the deeply supercooled state.     

Light scattering by longitudinal acoustic modes in supercooled molecular liquids II: microscopic derivation of the phenomenological equations

The constitutive equations for the orientational dynamics of a liquid formed of linear molecules are derived microscopically. The resulting generalised Langevin equations coincide with the phenomenological approach of Dreyfus et al. [1]. Formally exact expressions are given for the phenomenological coefficients and various constraints are shown to be consequences of this microscopic approach. Received 14 August 2002 Published online 4 February 2003 RID="a" ID="a"e-mail: franosch@hmi.de     

Decoupling phenomena in supercooled liquids: signatures in the energy landscape

A significant deviation from the Debye model of rotational diffusion in the dynamics of orientational degrees of freedom in an equimolar mixture of ellipsoids of revolution and spheres is found to begin at a temperature at which the average inherent structure energy of the system starts falling with drop in temperature. We argue that this onset temperature corresponds to the emergence of the process as a distinct mode of orientational relaxation. Further, we find that the coupling between rotational and translational diffusion breaks down at a still lower temperature where a change occurs in the temperature dependence of the average inherent structure energy.     

Origin of the high-frequency contributions to the dielectric loss in supercooled liquids

Dielectric loss spectra of four different glass formers revealing either beta relaxation or excess wing are presented. We compare the effect of pressure and temperature on the mentioned processes. Our findings suggest that the excess wing and the beta relaxation cannot be treated on the same footing.     

Atomic mechanism of glass formation in supercooled monatomic liquids

Atomic mechanism of glass formation in supercooled monatomic liquids is monitored via analyzing the spatial arrangement of solid-like atoms. The supercooled states are obtained by cooling from the melt using molecular dynamics (MD) simulation. Solid-like atoms, detected via Lindemann-like freezing criterion, are found throughout the liquid. Their number increases with decreasing temperature and they form clusters. In the deeply supercooled region, all solid-like atoms form a single percolation cluster which spans throughout the system. The number of atoms in this cluster increases steeply with further cooling. Glass formation in supercooled liquids occurs when a single percolation cluster of solid-like atoms involves the majority of atoms in the system to form a relatively rigid glassy solid. By analyzing the temperature dependence of static and dynamic properties, we identify three characteristic temperatures of glass formation in supercooled liquids including the Vogel–Fulcher temperature.     

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.     

Angular auto-correlation functions in molecular crystals and liquids: application to incoherent neutron scattering law

The effect of the local hindered molecular motion in the incoherent neutron scattering spectra in crystals and liquids is studied theoretically on the basis of the angular auto-correlation functions symmetrized on the dynamical point groups. The extended angular jump model simulates the motion. The microscopic properties of the matter, the time scale and the point symmetry of the molecule motion as well as the site symmetry of the molecule, are taken into account with the help of the dynamical variables of the model. The incoherent neutron scattering function is anisotropic in a monocrystalline sample. The scattering function consists of elastic plus quasi-elastic components. The shape of the quasi-elastic scattering spectrum is expressed by the sum of the weighted Lorentzian curves symmetrized with respect to the non-identical irreducible representations of the molecule motion point symmetry group. The elastic part of the intensity is increased by the contribution arising from the molecule motion of the identity representation symmetry. The scattering expression related to the molecule motion symmetry of a perfect cubic group is similar to the well-known expression derived for the scattering from the spherical top molecules exhibiting rotation diffusion.     

Pressure dependence of diffusion in simple glasses and supercooled liquids

Using molecular dynamics simulation, we have calculated the pressure dependence of the diffusion coefficient in a binary Lennard-Jones glass. We observe four temperature regimes. The apparent activation volume drops from high values in the hot liquid to a plateau value. Near the critical temperature of the mode coupling theory it rises steeply, but in the glassy state we find again small values, similar to the ones in the liquid. The peak of the activation volume at the critical temperature is in agreement with the prediction of mode coupling theory.     

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.