Structure and Thermodynamics of Binary Mixtures (Solutions)

The concepts of chapter 2 are generalized to binary liquid mixtures (solutions). With the help of the concept of number and concentration fluctuations contact to the thermodynamics of solutions and physical chemistry of solutions is made. The perturbative RPA is shown to be equivalent to Flory’s theory of regular solutions. The phase diagrams of regular solutions and metal-salt solutions are discussed and explained in terms of the theories.

Propagation and localisation of vibrational modes in 3–dimensional disordered systems: the binary force constant model

We consider a system of coupled harmonic oscillators on a cubic lattice. The force constants are supposed to take two distinct values at random according to a bond concentration x. The density of states (DOS) is evaluated both by numerical diagonalisation and in coherent-potential approximation (CPA). There is excellent agreement between the results of the two methods. Near the concentration, where the bonds with the larger force constants percolate, the DOS differs appreciably from the crystalline one and is anomalously enhanced at low frequencies as compared to Debye's ω2 law (“boson peak”). These features are shared with models with continuous distributions of force constants. The mean f…

Elastic torsion effects in magnetic nanoparticle diblock-copolymer structures

Magnetic properties of thin composite films, consisting of non-interacting polystyrene-coated γ-Fe(2)O(3) (maghemite) nanoparticles embedded into polystyrene-block-polyisoprene P(S-b-I) diblock-copolymer films are investigated. Different particle concentrations, ranging from 0.7 to 43 wt%, have been used. The magnetization measured as a function of external field and temperature shows typical features of anisotropic superparamagnets including a hysteresis at low temperatures and blocking phenomena. However, the data cannot be reconciled with the unmodified Stoner-Wohlfarth-Néel theory. Applying an appropriate generalization we find evidence for either an elastic torque being exerted on the …

Theory of vibrational anomalies in glasses

Abstract The theory of elasticity with spatially fluctuating elastic constants (heterogeneous-elasticity theory) is reviewed. It is shown that the vibrational anomalies associated with the boson peak can be qualitatively and quantitatively explained in terms of this theory. Two versions of a mean-field theory for solving the stochastic equation of motion are presented: the coherent-potential approximation (CPA) and the self-consistent Born approximation (SCBA). It is shown that the latter is included in the former in the Gaussian and weak-disorder limit. We are able to discuss and explain cases in which the change of the vibrational spectrum by varying an external parameter can be accounted…

Anharmonic elasticity theory for sound attenuation in disordered solids with fluctuating elastic constants

The boson peak

The vibrational properties of glasses in the THz range differ very much from what is expected from Debye's elasticity theory: the density of states (DOS) deviates from Debye's ω2 law [the “boson peak” (BP)], the sound velocity shows a negative dispersion in the BP frequency regime and there is a strong increase in the sound attenuation near the BP frequency. These anomalies are related to an anomalous temperature dependence of the specific heat and thermal conductivity in the 10 K regime. An overview of the heterogeneous-elasticity theory is given, by means of which all these anomalies can be explained and shown to arise from the structural disorder, leading to spatial fluctuations of the s…

Sound attenuation and anharmonic damping in solids with correlated disorder

We study via self-consistent Born approximation a model for sound waves in a disordered environment, in which the local fluctuations of the shear modulus G are spatially correlated with a certain correlation length The theory predicts an enhancement of the density of states over Debye's omega(2) law (boson peak) whose intensity increases for increasing correlation length, and whose frequency position is shifted downwards as lg. Moreover, the predicted disorder-induced sound attenuation coefficient r(k) obeys a universal scaling law F(k) = f (ke) for a given variance of G. Finally, the inclusion of the lowest-order contribution to the anharmonic sound damping into the theory allows us to rec…

Acoustic dynamics of network-forming glasses at mesoscopic wavelengths

The lack of long-range structural order in amorphous solids induces well known thermodynamic anomalies, which are the manifestation of distinct peculiarities in the vibrational spectrum. Although the impact of such anomalies vanishes in the long wavelength, elastic continuum limit, it dominates at length scales comparable to interatomic distances, implying an intermediate transition regime still poorly understood. Here we report a study of such mesoscopic domains by means of a broadband version of picosecond photo-acoustics, developed to coherently generate and detect hypersonic sound waves in the sub-THz region with unprecedented sampling efficiency. We identify a temperature-dependent fra…

What is the Right Theory for Anderson Localization of Light? An Experimental Test

Anderson localization of light is traditionally described in analogy to electrons in a random potential. Within this description, the random potential depends on the wavelength of the incident light. For transverse Anderson localization, this leads to the prediction that the distribution of localization lengths---and, hence, its average---strongly depends on the wavelength. In an alternative description, in terms of a spatially fluctuating electric modulus, this is not the case. Here, we report on an experimentum crucis in order to investigate the validity of the two conflicting theories using optical samples exhibiting transverse Anderson localization. We do not find any dependence of the …

Anomalous magneto-transport in disordered structures: classical edge-state percolation

By event-driven molecular dynamics simulations we investigate magneto-transport in a two-dimensional model with randomly distributed scatterers close to the field-induced localization transition. This transition is generated by percolating skipping orbits along the edges of obstacle clusters. The dynamic exponents differ significantly from those of the conventional transport problem on percolating systems, thus establishing a new dynamic universality class. This difference is tentatively attributed to a weak-link scenario, which emerges naturally due to barely overlapping edge trajectories. We make predictions for the frequency-dependent conductivity and discuss implications for active coll…

Theory of heterogeneous viscoelasticity

We review a new theory of viscoelasticity of a glass-forming viscous liquid near and below the glass transition. In our model we assume that each point in the material has a specific viscosity, which varies randomly in space according to a fluctuating activation free energy. We include a Maxwellian elastic term and assume that the corresponding shear modulus fluctuates as well with the same distribution as that of the activation barriers. The model is solved in coherent-potential approximation (CPA), for which a derivation is given. The theory predicts an Arrhenius-type temperature dependence of the viscosity in the vanishing-frequency limit, independent of the distribution of the activatio…

Analytical description of the transverse Anderson localization of light

Replica field theory for anharmonic sound attenuation in glasses

Abstract A saddle-point treatment of interacting phonons in a disordered environment is developed. In contrast to crystalline solids, anharmonic attenuation of density fluctuations becomes important in the hydrodynamic regime, due to a broken momentum conservation. The variance of the shear modulus Δ2 turns out to be the strength of the disorder enhanced phonon–phonon interaction. In the low-frequency regime (below the boson peak frequency) we obtain an Akhiezer-like sound attenuation law Γ ∝ Τω2. Together with the usual Rayleigh scattering mechanism this yields a crossover of the Brillouin linewidth from a ω2 to a ω4 regime. The crossover frequency ωc is fully determined by the boson peak …

Time-Dependent Correlation and Response Functions

The dynamics of liquids is discussed with the help of time-dependent correlation functions. They are related to response functions by the fluctuation-dissipation theorem. This theorem enables to relate experimentally measured inelastic scattering data to the Fourier-transformed correlation and response functions. The Laplace transform of the correlation functions can be represented as a continuous fraction with suitable residual terms (memory functions). The projection formalism of Mori and Zwanzig is introduced.

Electronic correlation effects and the Coulomb gap at finite temperature.

We have investigated the effect of the long-range Coulomb interaction on the one-particle excitation spectrum of n-type Germanium, using tunneling spectroscopy on mechanically controllable break junctions. The tunnel conductance was measured as a function of energy and temperature. At low temperatures, the spectra reveal a minimum at zero bias voltage due to the Coulomb gap. In the temperature range above 1 K the Coulomb gap is filled by thermal excitations. This behavior is reflected in the temperature dependence of the variable-range hopping resitivity measured on the same samples: Up to a few degrees Kelvin the Efros-Shkovskii ln$R \propto T^{-1/2}$ law is obeyed, whereas at higher tempe…

Disentangling boson peaks and Van Hove singularities in a model glass

Using the example of a two-dimensional macroscopic model glass in which the interparticle forces can be precisely measured, we obtain strong hints for resolving a controversy concerning the origin of the anomalous enhancement of the vibrational spectrum in glasses (boson peak). Whereas many authors attribute this anomaly to the structural disorder, some other authors claim that the short-range order, leading to washed-out Van Hove singularities, would cause the boson-peak anomaly. As in our model system, the disorder-induced and shortrange--order-induced features can be completely separated, we are able to discuss the controversy about the boson peak in real glasses in a new light. Our find…

Disorder-induced vibrational anomalies from crystalline to amorphous solids

The origin of boson peak -- an excess of density of states over Debye's model in glassy solids -- is still under intense debate, among which some theories and experiments suggest that boson peak is related to van-Hove singularity. Here we show that boson peak and van-Hove singularity are well separated identities, by measuring the vibrational density of states of a two-dimensional granular system, where packings are tuned gradually from a crystalline, to polycrystals, and to an amorphous material. We observe a coexistence of well separated boson peak and van-Hove singularities in polycrystals, in which the van-Hove singularities gradually shift to higher frequency values while broadening th…

Diffusive Motion in Simple Liquids

The diffusive motion of single particles in a simple liquids is shown to be related to the incoherent part of the neutron-scattering cross-section. Miscallaneous topics concerning the diffusive motion are discussed.

Disorder-induced single-mode transmission.

Localized states trap waves propagating in a disordered potential and play a crucial role in Anderson localization, which is the absence of diffusion due to disorder. Some localized states are barely coupled with neighbours because of differences in wavelength or small spatial overlap, thus preventing energy leakage to the surroundings. This is the same degree of isolation found in the homogeneous core of a single-mode optical fibre. Here we show that localized states of a disordered optical fibre are single mode: the transmission channels possess a high degree of resilience to perturbation and invariance with respect to the launch conditions. Our experimental approach allows identification…

Do we understand the solid-like elastic properties of confined liquids?

Recently, in polymeric liquids, unexpected solid-like shear elasticity has been discovered, which gave rise to a controversial discussion about its origin (1⇓–3). The observed solid-like shear modulus G depends strongly on the distance L between the plates of the rheometer according to a power law G ∝ L − p with a nonuniversal exponent ranging between p = 2 and p = 3 . Zaccone and Trachenko (4) have published an article in which they claim to explain these findings by a nonaffine contribution to the liquid shear modulus. The latter is represented as Δ G ∝ − ∑ λ = L , T 1 V … [↵][1]1To whom correspondence may be addressed. Email: giancarlo.ruocco{at}roma1.infn.it. [1]: #xref-corresp-1-1

Structure of Liquids

An Introduction to the description of the static structure of simple liquids is given. The principle quantity, which describes this structure is the structure factor, which can be measured with neutron and X-ray diffraction. The structure factor is the Fourier transform of the radial pair distribution function, which describes the statistics of the atoms around a given one. Several theories are introduced for calculating this quantities. It is shown that the structure of liquid metals is dominated by their hardcore repulsion. In the low-wavenumber limit the structure factor is related to the compressibility of the liquid. In this limit deviations from the hard-core model become importent, w…

Inelastic neutron and low-frequency Raman scattering in niobium-phosphate glasses: the role of spatially fluctuating elastic and elasto-optic constants

We investigate the low-frequency enhancement of vibrational excitations ('boson peak') in niobium-phosphate glasses through the combination of inelastic neutron and polarization-resolved Raman scattering. The spectra of these glasses reveal an enhancement of the vibrational density of states and of the cross section for spontaneous Raman scattering in the frequency range below 150?cm ? 1. A recent theoretical model that is based on fluctuating elastic and elasto-optic (Pockels) constants provides a unified description of the measured neutron and Raman spectra, including the depolarization ratio.

Self-consistent Euclidean-random-matrix theory

Some comments on fluctuating-elasticity and local oscillator models for anomalous vibrational excitations in glasses

Abstract An overview is given on the present status of the theoretical description of vibrational spectra of glasses, as seen by inelastic neutron, X-ray and light (Raman) scattering. Using the language of Green's/response functions the merits and shortcomings of a local oscillator and a generalized elasticity-theory point of view are discussed. It is pointed out that in both cases the interaction of phonons with disorder-induced irregularities leads to Rayleigh scattering (mean free path l ∝ ω − 4 ) at low enough frequencies and temperatures. In disordered solids at ambient temperature the Rayleigh scattering is usually masqued by Akhiezer-like anharmonic scattering l ∝ ω − 2 , but it can …

Random Walk and Diffusion

The concept of random walk as introduced by Einstein is introduced. It is shown that a random walk on a lattice can be descrbed by a difference equation, which becomes a partial differential equation (diffusion equation) in the continuum limit. The equation is solved with the help of Fourier and Laplace transformations.

Coherent potential approximation for diffusion and wave propagation in topologically disordered systems

Using Gaussian integral transform techniques borrowed from functional-integral field theory and the replica trick we derive a version of the coherent-potential approximation (CPA) suited for describing ($i$) the diffusive (hopping) motion of classical particles in a random environment and ($ii$) the vibrational properties of materials with spatially fluctuating elastic coefficients in topologically disordered materials. The effective medium in the present version of the CPA is not a lattice but a homogeneous and isotropic medium, representing an amorphous material on a mesoscopic scale. The transition from a frequency-independent to a frequency-dependent diffusivity (conductivity) is shown …

Level statistics and Anderson delocalization in two-dimensional granular materials

Contrary to the theoretical predictions that all waves in two-dimensional disordered materials are localized, Anderson localization is observed only for sufficiently high frequencies in an isotropically jammed two-dimensional disordered granular packing of photoelastic disks. More specifically, we have performed an experiment in analyzing the level statistics of normal mode vibrations. We observe delocalized modes in the low-frequency boson-peak regime and localized modes in the high frequency regime with the crossover frequency just below the Debye frequency. We find that the level-distance distribution obeys Gaussian-Orthogonal-Ensemble (GOE) statistics, i.e. Wigner-Dyson distribution, in…

Heterogeneous shear elasticity of glasses: the origin of the boson peak

The local elasticity of glasses is known to be inhomogeneous on a microscopic scale compared to that of crystalline materials. Their vibrational spectrum strongly deviates from that expected from Debye's elasticity theory: The density of states deviates from Debye's law, the sound velocity shows a negative dispersion in the boson-peak frequency regime and there is a strong increase of the sound attenuation near the boson-peak frequency. By comparing a mean-field theory of shear-elastic heterogeneity with a large-scale simulation of a soft-sphere glass we demonstrate that the observed anomalies in glasses are caused by elastic heterogeneity. By observing that the macroscopic bulk modulus is …

High-field nuclear spin relaxation in liquids and solids

The authors generalise the standard theory of nuclear spin relaxation to situations in which the Markovian approximation is not applicable. Expressions for generalised frequency-dependent spin relaxation functions are presented. They show that under high-field conditions the relaxation of longitudinal magnetisation is exponential independent of the particular time dependence of the correlation functions.

Structure of Polymers

The structure and thermodynamics of polymers are discussed both with an adapted version of Flory’s regular solution theory and the concept of scaling and random walks. The salient properties of polymers like segregation and elasticity are discussed in terms of these concept. The Flory-Stockmayer theory of gelation is introduced and related to the percolation concept.

Schmid and Schirmacher Reply:

Comment on "Universal Origin of Boson Peak Vibrational Anomalies in Ordered Crystals and in Amorphous Materials".

Disorder Classification of the Vibrational Spectra of Modern Glasses

Using the coherent-potential approximation in heterogeneous-elasticity theory with a log-normal distribution of elastic constants for the description of the Raman spectrum and the temperature dependence of the specifi?c heat, we are able to reconstruct the vibrational density of states and characteristic descriptors of the elastic heterogeneity of a wide range of glassy materials. These descriptors are the non-affi?ne contribution to the shear modulus, the mean-square fluctuation of the local elasticity, and its correlation length. They enable a physical classification scheme for disorder in modern, industrially relevant glass materials. We apply our procedure to a broad range of real-world…

An equation of state for expanded metals.

We present a model equation of states for expanded metals, which contains a pressure term due to a screened-Coulomb potential with a screening parameter reflecting the Mott-Anderson metal-to-nonmetal transition. As anticipated almost 80 years ago by Zel'dovich and Landau, this term gives rise to a second coexistence line in the phase diagram, indicating a phase separation between a metallic and a nonmetallic liquid.

Euclidean random matrix theory: low-frequency non-analyticities and Rayleigh scattering

By calculating all terms of the high-density expansion of the euclidean random matrix theory (up to second-order in the inverse density) for the vibrational spectrum of a topologically disordered system we show that the low-frequency behavior of the self energy is given by $\Sigma(k,z)\propto k^2z^{d/2}$ and not $\Sigma(k,z)\propto k^2z^{(d-2)/2}$, as claimed previously. This implies the presence of Rayleigh scattering and long-time tails of the velocity autocorrelation function of the analogous diffusion problem of the form $Z(t)\propto t^{(d+2)/2}$.

Glass Transition and Glass Dynamics

The transition from an undercooled liquid towards a glass (glass transition) is introduced and discussed in terms of mode-coupling theory. It is demonstrated that mode-coupling theory leads to a two-step relaxation scenario near the transition with time-critical exponents, which characterize the two relaxation steps (beta and alpha relaxation). The anomalous vibrational properties of a disordered solid (glass) is explained in terms of a model with spatially fluctuating harmonic force constants.

Vibrational excitations in systems with correlated disorder

We investigate a $d$-dimensional model ($d$ = 2,3) for sound waves in a disordered environment, in which the local fluctuations of the elastic modulus are spatially correlated with a certain correlation length. The model is solved analytically by means of a field-theoretical effective-medium theory (self-consistent Born approximation) and numerically on a square lattice. As in the uncorrelated case the theory predicts an enhancement of the density of states over Debye's $\omega^{d-1}$ law (``boson peak'') as a result of disorder. This anomay becomes reinforced for increasing correlation length $\xi$. The theory predicts that $\xi$ times the width of the Brillouin line should be a universal …

Model calculations for vibrational properties of disordered solids and the “boson peak”

Abstract It is demonstrated that a disordered system of coupled classical harmonic oscillators with a continuous distribution of coupling parameters exhibits generally a low-frequency enhancement (“boson peak”) of the density of states, as compared with the Debye law. This phenomenon is most pronounced if the system is close to an instability. This is shown by means of a scalar model on a simple cubic lattice. The force constants are assumed to fluctuate from bond to bond according to a Gaussian distribution which is truncated at its lower end. The model is solved for the density of states and the one-phonon dynamic structure factor S(q, ω) by applying the two-site coherent potential approx…

Rayleigh and Brillouin scattering in a lysozyme–water mixture: An unusual behavior around 343K

Abstract This article describes Rayleigh and Brillouin light scattering studies on a lysozyme–water mixture from 293 K to 355 K. The scattering intensities from this system are compared with those from a sodium acetate buffer used to dissolve the lysozyme. It is found that in the vicinity of 343 K the lysozyme–water mixture becomes opalescent, and the intensity of the Brillouin peaks decreases and almost vanishes, to be restored at temperatures above 343 K. Around the same temperature the intensity of the central, unshifted Rayleigh peak, however, increases strongly. No such behavior was observed for the sodium acetate buffer. The analysis of the experimental data indicates an irreversible …

Localization-delocalization transition for disordered cubic harmonic lattices.

We study numerically the disorder-induced localization-delocalization phase transitions that occur for mass and spring constant disorder in a three-dimensional cubic lattice with harmonic couplings. We show that, while the phase diagrams exhibit regions of stable and unstable waves, the universality of the transitions is the same for mass and spring constant disorder throughout all the phase boundaries. The combined value for the critical exponent of the localization lengths of $\nu = 1.550^{+0.020}_{-0.017}$ confirms the agreement with the universality class of the standard electronic Anderson model of localization. We further support our investigation with studies of the density of states…

Modified mode-coupling theory for the collective dynamics of simple liquids

Recently it has been shown that mode-coupling theory, which accounts for the salient features of glassy relaxation near the liquid–glass transition, is also capable of describing the collective excitations of simple liquids away from the glass transition. In order to further improve the agreement between theory and computer simulations on Lennard-Jones argon we modify MCT by taking binary collisions into account. This, in fact, improves the agreement. We also show that multiplying the memory function of the original theory with a reduction factor leads to similar results.

Inelastic neutron and low-frequency Raman scattering in a niobium-phosphate glass for Raman gain applications

Abstract We present measurements of the vibrational spectrum of a binary niobium-phosphate glass in the THz frequency range using inelastic neutron and Raman scattering. The spectra of these glasses show a low-frequency enhancement of the vibrational density of states (“boson peak”). Using a recently developed theory of vibrational excitations in disordered solids we are able to reconcile the measured neutron and Raman spectra using fluctuating elastic and Pockels constants as a model concept. As the spontaneous Raman susceptibility is a key parameter for Raman amplification our results suggest a significant gain profile for application of niobium-phosphate glasses in Raman amplifiers.

Conclusions: Take-Home Messages

In this chapter, which mainly consists of headlines, the take-home messages of the lecture notes are presented.

Harmonic Vibrational Excitations in Disordered Solids and the "Boson Peak"

We consider a system of coupled classical harmonic oscillators with spatially fluctuating nearest-neighbor force constants on a simple cubic lattice. The model is solved both by numerically diagonalizing the Hamiltonian and by applying the single-bond coherent potential approximation. The results for the density of states $g(\omega)$ are in excellent agreement with each other. As the degree of disorder is increased the system becomes unstable due to the presence of negative force constants. If the system is near the borderline of stability a low-frequency peak appears in the reduced density of states $g(\omega)/\omega^2$ as a precursor of the instability. We argue that this peak is the anal…

High-frequency vibrational density of states of a disordered solid.

We investigate the high-frequency behavior of the density of vibrational states in three-dimensional elasticity theory with spatially fluctuating elastic moduli. At frequencies well above the mobility edge, instanton solutions yield an exponentially decaying density of states. The instanton solutions describe excitations, which become localized due to the disorder-induced fluctuations, which lower the sound velocity in a finite region compared to its average value. The exponentially decaying density of states (known in electronic systems as the Lifshitz tail) is governed by the statistics of a fluctuating-elasticity landscape, capable of trapping the vibrational excitations.

Collective Excitations in Simple Liquids

The dynamics of simple liquid is discussed by starting from the linearized Navier-Stokes equations. Using these equations expicit formulas for the density- and current-correlation functions are given. Mode-coupling theory is introduced, which gives a constitutive equation between the current-relaxation memory function and the density correlation function. This theory is shown to accurately describe the collective-excitation behavior of simple liquids like liquid metals.

Continuum constitutive laws to describe acoustic attenuation in glasses

International audience; Nowadays metamaterials are at the focus of an intense research as promising for thermal and acoustic engineering. However, the computational cost associated to the large system size required for correctly simulating them imposes the use of finite-elements simulations, developing continuum models, able to grasp the physics at play without entering in the atomistic details. Still, a correct description should be able to reproduce not only the extrinsic scattering sources on waves propagation, as introduced by the metamaterial microstructure, but also the intrinsic wave attenuation of the material itself. This becomes dramatically important when the metamaterial is made…