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Alessio Zaccone

Publications and source records attributed to Alessio Zaccone.

At least 127 records · Page 7Linked to original sources

A new paradigm for the low-T glassy-like thermal properties of solids

Glasses and disordered materials are known to display anomalous features in the density of states, in the specific heat and in thermal transport. Nevertheless, in recent years, the question whether these properties are really anomalous (and peculiar of disordered systems) or rather more universal than previously thought, has emerged. New experimental and theoretical observations have questioned the origin of the boson peak and the linear in T specific heat exclusively from disorder and TLS. The same properties have been indeed observed in ordered or minimally disordered compounds and in incommensurate structures for which the standard explanations are not applicable. Using the formal analogy between phason modes (e.g. in quasicrystals and incommensurate lattices) and diffusons, and between amplitude modes and optical phonons, we suggest the existence of a more universal physics behind these properties. In particular, we strengthen the idea that linear in T specific heat is linked to low energy diffusive modes and that a BP excess can be simply induced by gapped optical-like modes.

cond-mat.dis-nn↗

Predictive model of polymer reaction kinetics and coagulation behavior in seeded emulsion co- and ter-polymerizations

A mathematical model to describe the emulsion polymerization kinetics of co- and ter-polymerizations is developed. The model is based on the classical Smith-Ewart (SE) equations, within the pseudo-homopolymerization approach, with state-of-the-art models for radical entry and desorption. For co- and ter-polymerizations there are unknown parameters in the model which are related to monomer-specific gel-effect coefficients, that are needed to compute the bimolecular termination reaction rates. The unknown parameters are determined through extensive calibration of the model on literature data for homo- and co-polymerizations of \textit{n}-butyl acrylate (n-BA) and methyl methacrylate (MMA). The so-obtained predictive model is then applied to the modelling of the ter-polymerization of n-BA and MMA with 2-hydroxyethyl methacrylate (2-HEMA) with sodium persulphate (SPR) as initiator: predictions for the time-evolution of particle size and conversion are in excellent agreement with experimental measurements using Dynamic Light Scattering (DLS) and Gas Chromatography (GC), upon tuning the gel-effect coefficient related to 2-HEMA. The developed model is used to quantify the surfactant surface coverage of the particles as well as the total concentration of counterions in the system throughout the entire polymerization process. This key information provides a way to rationalize and control the coagulation behavior during the whole polymerization process.

physics.chem-ph↗

Scaling up the lattice dynamics of amorphous materials by orders of magnitude

We generalise the non-affine theory of viscoelasticity for use with large, well-sampled systems of arbitrary chemical complexity. Having in mind predictions of mechanical and vibrational properties of amorphous systems with atomistic resolution, we propose an extension of the Kernel Polynomial Method (KPM) for the computation of the vibrational density of states (VDOS) and the eigenmodes, including the $Γ$-correlator of the affine force-field, which is a key ingredient of lattice-dynamic calculations of viscoelasticity. We show that the results converge well to the solution obtained by direct diagonalization (DD) of the Hessian (dynamical) matrix. As is well known, the DD approach has prohibitively high computational requirements for systems with $N=10^4$ atoms or larger. Instead, the KPM approach developed here allows one to scale up lattice dynamic calculations of real materials up to $10^6$ atoms, with a hugely more favorable (linear) scaling of computation time and memory consumption with $N$.

cond-mat.dis-nn↗

Atomic-scale expressions for viscosity and fragile-strong behavior in metal alloys based on the Zwanzig-Mountain formula

We combine the shoving model of $T$-dependent viscosity of supercooled liquids with the Zwanzig-Mountain formula for the high-frequency shear modulus, using the $g(r)$ of MD simulations of metal alloys as the input. This scheme leads to a semi-analytical expression for the viscosity as a function of temperature, which provides a three-parameter model fitting of experimental data of viscosity for the same alloy for which $g(r)$ was calculated. The model provides direct access to the influence of atomic-scale physical quantities such as the interatomic potential $ϕ(r)$, on the viscosity and fragile-strong behavior. In particular, it is established that a steeper interatomic repulsion leads to fragile liquids, or, conversely, that "soft atoms make strong liquids".

cond-mat.soft↗

Nonequilibrium continuous phase transition in colloidal gelation with short-range attraction

The dynamical arrest of attractive colloidal particles into out-of-equilibrium structures, known as gelation, is central to biophysics, materials science, nanotechnology, and food and cosmetic applications, but a complete understanding is lacking. In particular, for intermediate particle density and attraction, the structure formation process remains unclear. Here, we show that the gelation of short-range attractive particles is governed by a nonequilibrium percolation process. We combine experiments on critical Casimir colloidal suspensions, numerical simulations, and analytical modeling with a master kinetic equation to show that cluster sizes and correlation lengths diverge with exponents 1.6 and 0.8, respectively, consistent with percolation theory, while detailed balance in the particle attachment and detachment processes is broken. Cluster masses exhibit power-law distributions with exponents -3/2 and -5/2 before and after percolation, as predicted by solutions to the master kinetic equation. These results revealing a nonequilibrium continuous phase transition unify the structural arrest and yielding into related frameworks.

cond-mat.soft↗

Rheology of Hard Glassy Materials

Glassy solids may undergo a fluidization (yielding) transition upon deformation whereby the material starts to flow plastically. It has been a matter of debate whether this process is controlled by a specific time scale, from among different competing relaxation/kinetic processes. Here, two constitutive models of cage relaxation are examined within the microscopic model of nonaffine elasto-plasticity. One (widely used) constitutive model implies that the overall relaxation rate is dominated by the fastest between the structural ($α$) relaxation rate and the shear-induced relaxation rate. A different model is formulated here which, instead, assumes that the slowest (global) relaxation process controls the overall relaxation. We show that the first model is not compatible with the existence of finite elastic shear modulus for quasistatic (low-frequency) deformation, while the second model is able to describe all key features of deformation of `hard' glassy solids, including the yielding transition, the nonaffine-to-affine plateau crossover, and the rate-stiffening of the modulus. The proposed framework provides an operational way to distinguish between `soft' glasses and `hard' glasses based on the shear-rate dependence of the structural relaxation time.

cond-mat.soft↗

Effective Theory of Superconductivity in Strongly-Coupled Amorphous Materials

A theory of phonon-mediated superconductivity in strong-coupling amorphous materials is developed based on an effective description of structural disorder and its effect on the vibrational spectrum. The theory accounts for the diffusive-like transport of vibrational excitations due to disorder-induced scattering within the Eliashberg theory of strong-coupling superconductivity. The theory provides a good analytical description of the Eliashberg function $α^{2}F(ω)$ in comparison with experiments, and allows one to disentangle the effects of transverse and longitudinal excitations on the Eliashberg function. In particular, it shows that the transverse excitations play a crucial role in driving an increase or excess in the Eliashberg function at low energy, which is related to the boson peak phenomenon in vibrational spectra of glasses. This low-energy excess, on one hand drives an enhancement of the electron-phonon coupling but at the same time reduces the characteristic energy scale $ω_{log}$ in the Allen-Dynes formula. As a consequence, the non-monotonicity of $T_{c}$ as a function of alloying (disorder) in $\text{Pb}$-based systems can be rationalized. The case of $\text{Al}$-based systems, where disorder increases $T_{c}$ from the start, is also analyzed. General material-design principles for enhancing $T_{c}$ in amorphous superconductors are presented.

cond-mat.supr-con↗

Physics of Phonon-Polaritons in Amorphous Materials

The nature of bosonic excitations in disordered materials has remained elusive due to the difficulties in defining key concepts such as quasi-particles in the presence of disorder. We report on the experimental observation of phonon-polaritons in glasses, including a boson peak (BP), i.e. excess of THz modes over the Debye law. A theoretical framework based on the concept of diffusons is developed to model the broadening linewidth of the polariton due to disorder-induced scattering. It is shown that the scaling of the BP frequency with the diffusion constant of the linewidth strongly correlates with that of the Ioffe-Regel (IR) crossover frequency of the polariton. This result demonstrates the universality of the BP in the low-energy spectra of collective bosonic-like excitations in glasses, well beyond the traditional case of acoustic phonons, and establishes the IR crossover as the fundamental physical mechanism behind the BP.

cond-mat.dis-nn↗

Secondary relaxation in the terahertz range in 2-adamantanone from theory and experiments

We applied the recently developed Generalized Langevin Equation (GLE) approach for dielectric response of liquids and glasses to link the vibrational density of states (VDOS) to the dielectric response of a model orientational glass (OG). The dielectric functions calculated based on the GLE, with VDOS obtained in experiments and simulations as inputs, are compared with experimental data for the paradigmatic case of 2-adamantanone at various temperatures. The memory function is related to the integral of the VDOS times a spectral coupling function $γ(ω_p)$, which tells the degree of dynamical coupling between molecular degrees of freedom at different eigenfrequencies. With respect to previous empirical fittings, the GLE-based fitting reveals a broader temperature range over which the secondary relaxation is active. Furthermore, the theoretical analysis provides a clear evidence of secondary relaxation being localized within the THz ($0.5-1$ THz) range of eigenfrequencies, and thus not too far from the low-energy modes involved in $α$-relaxation. In the same THz region, the same material displays a crowding of low-energy optical modes that may be related to the secondary relaxation.

cond-mat.soft↗

Relaxation and vibrational properties in metal alloys and other disordered systems

The relaxation dynamics and the vibrational spectra of amorphous solids, such as metal alloys, have been intensely investigated as well separated topics in the past. The aim of this review is to summarize recent results in both these areas in an attempt to establish, or unveil, deeper connections between the two phenomena of relaxation and vibration. Theoretical progress in the area of slow relaxation dynamics of liquid and glassy systems and in the area of vibrational spectra of glasses and liquids is reviewed. After laying down a generic modelling framework to connect vibration and relaxation, the physics of metal alloys is considered where the emergence of power-law exponents has been identified both in the vibrational density of states (VDOS) as well as in density correlations. Also, theoretical frameworks which connect the VDOS to the relaxation behaviour and mechanical viscoelastic response in metallic glasses are reviewed. The same generic interpretative framework is then applied to the case of molecular glass formers where the emergence of stretched-exponential relaxation in dielectric relaxation can be put in quantitative relation with the VDOS by means of memory-function approaches. Further connections between relaxation and vibration are provided by the study of phonon linewidths in liquids and glasses, where a natural starting point is given by hydrodynamic theories. Finally, an agenda of outstanding issues including the appearance of compressed exponential relaxation in the intermediate scattering function of experimental and simulated systems (metal alloys, colloidal gels, jammed packings) is presented in light of available (or yet to be developed) mathematical models, and compared to non-exponential behaviour measured with macroscopic means such as mechanical spectroscopy/rheology.

cond-mat.mtrl-sci↗

Theory of the phonon spectrum in host-guest crystalline solids with avoided crossing

We develop an analytical model to describe the phonon dispersion relations of host-guest lattices with heavy guest atoms (rattlers). Crucially, the model also accounts for phonon damping arising from anharmonicity. The spectrum of low energy states contains acoustic-like and (soft) optical-like modes, which display the typical avoided crossing, and which can be derived analytically by considering the dynamical coupling between host lattice and guest rattlers. Inclusion of viscous anharmonic damping in the model allows us, for the first time, to compute the vibrational density of states (VDOS) and the specific heat, unveiling the presence of a boson peak (BP) linked to an anharmonicity-smeared van Hove singularity. Upon increasing the coupling strength between the host and the guest dynamics, and by decreasing the energy of the soft optical modes, the BP anomaly becomes stronger and it moves towards lower frequencies. Moreover, we find a robust linear correlation between the BP frequency and the energy of the soft optical-like modes. This framework provides a useful model for tuning the thermal properties of host-guest lattices by controlling the VDOS, which is crucial for optimizing thermal conductivity and hence the energy conversion efficiency in these materials.

cond-mat.mtrl-sci↗

Atomistic structural mechanism for the glass transition: Entropic contribution

A popular Adam--Gibbs scenario has suggested that the excess entropy of glass and liquid over crystal dominates the dynamical arrest at the glass transition with exclusive contribution from configurational entropy over vibrational entropy. However, an intuitive structural rationale for the emergence of frozen dynamics in relation to entropy is still lacking. Here we study these issues by atomistically simulating the vibrational, configurational, as well as total entropy of a model glass former over their crystalline counterparts for the entire temperature range spanning from glass to liquid. Besides confirming the Adam--Gibbs entropy scenario, the concept of Shannon information entropy is introduced to characterize the diversity of atomic-level structures, which undergoes a striking variation across the glass transition, and explains the change found in the excess configurational entropy. Hence, the hidden structural mechanism underlying the entropic kink at the transition is revealed in terms of proliferation of certain atomic structures with a higher degree of centrosymmetry, which are more rigid and possess less nonaffine softening modes. In turn, the proliferation of these centrosymmetric (rigid) structures leads to the freezing-in of the dynamics beyond which further structural rearrangements become highly unfavourable, thus explaining the kink in the configurational entropy at the transition.

cond-mat.soft↗

Unified theory of vibrational spectra in amorphous materials

The phonon spectra of solids, described through the measurable vibrational density of states (VDOS), provide a wealth of information about the underlying atomic structure and bonding, and they determine fundamental macroscopic properties such as specific heat, thermal conductivity and superconductivity. In amorphous solids, structural disorder generates a number of poorly understood phenomena that are absent in crystals. Starting from an effective field theory description which accounts for disorder in terms of momentum diffusion, we provide a unified theoretical description of the VDOS of amorphous materials. The theory provides an excellent description of the simulated/experimental VDOS of two quite different materials (silica glass and amorphous Si) with very few non-trivial fitting parameters. In particular, the phonons speeds and diffusive linewidths obtained from the fits are fully consistent with the tabulated values from experiments. This semi-analytical approach solves the long-standing problem of describing and explaining the features of the VDOS and Raman spectra of amorphous solids in relation with the underlying acoustic dispersion relations and acoustic attenuation. Furthermore, it can be used in a reverse-engineered way to estimate phonon dispersion relations, acoustic attenuation and dynamic structure factors from a simple fitting of the VDOS with the presented model.

cond-mat.mtrl-sci↗

Identifying non-affine softening modes in glassy polymer networks: A pathway to chemical design

Using molecular simulations and theory, we develop an explicit mapping of the contribution of molecular relaxation modes in glassy thermosets to the shear modulus, where the relaxations were tuned by altering the polarity of side groups. Specifically, motions at the domain, segmental, monomer, and atomic levels are taken from molecular dynamics snapshots and directly linked with the viscoelasticity through a framework based in the lattice dynamics of amorphous solids. This unique approach provides direct insight into the roles of chemical groups in the stress response, including the timescale and spatial extent of relaxations during mechanics. Two thermoset networks with differing concentrations of polar side groups were examined, dicyclopentadiene (DCPD) and 5-norbornene-2-methanol (NBOH). A machine learning method is found to be effective for quantifying large-scale correlated motions while more local chemical relaxations are readily identified by direct inspection. The approach is broadly applicable and enables rapid predictions of the frequency-dependent modulus for any glass.

cond-mat.mtrl-sci↗

Nonaffine lattice dynamics with the Ewald method reveals strongly nonaffine elasticity of α-quartz

A lattice dynamical formalism based on nonaffine response theory is derived for non-centrosymmetric crystals, accounting for long-range interatomic interactions using the Ewald method. The framework takes equilibrated static configurations as input to compute the elastic constants in excellent agreement with both experimental data and calculations under strain. Besides this methodological improvement, which enables faster evaluation of elastic constants without the need of explicitly simulating the deformation process, the framework provides insights into the nonaffine contribution to the elastic constants of α-quartz. It turns out that, due to the non-centrosymmetric lattice structure, the nonaffine (softening) correction to the elastic constants is very large, such that the overall elastic constants are at least 3-4 times smaller than the affine Born-Huang estimat

cond-mat.mtrl-sci↗

Hydrodynamics of disordered marginally-stable matter

We study the vibrational spectra and the specific heat of disordered systems using an effective hydrodynamic framework. We consider the contribution of diffusive modes, i.e. the 'diffusons', to the density of states and the specific heat. We prove analytically that these new modes provide a constant term to the vibrational density of states $g(ω)$. This contribution is dominant at low frequencies, with respect to the Debye propagating modes. We compare our results with numerical simulations data and random matrix theory. Finally, we compute the specific heat and we show the existence of a linear in $T$ scaling $C(T) \sim c\,T$ at low temperatures due to the diffusive modes. We analytically derive the coefficient $c$ in terms of the diffusion constant $D$ of the quasi-localized modes and we obtain perfect agreement with numerical data. The linear in $T$ behavior in the specific heat is stronger the more localized the modes, and crosses over to a $T^{3}$ (Debye) regime at a temperature $T^{*}\sim \sqrt{v^{3}/D}$, where $v$ is the speed of sound. Our results suggest that the anomalous properties of glasses and disordered systems can be understood effectively within a hydrodynamic approach which accounts for diffusive quasi-localized modes generated via disorder-induced scattering.

cond-mat.dis-nn↗

Infrasonic wave propagation in ultrasoft solids at low Reynolds numbers

The propagation of elastic waves in soft materials plays a crucial role in the spatio-temporal transmission of mechanical signals, e.g. in biological mechanotransduction or in the failure of marginal solids. At high Reynolds numbers $Re \gg 1$, inertia dominates and wave propagation can be readily observed. However, mechanical cues in soft and biological materials often occur at low $Re$, where waves are overdamped. Not only have low $Re$ waves been difficult to observe in experiments, their theoretical description remains incomplete. In this paper, we present direct measurements of low $Re$ waves propagating in ordered and disordered soft solids, generated by an oscillating point force induced by an optical trap. We derive an analytical theory for low $Re$ wave propagation, which is in excellent agreement with the experiments. Our results present both a new method to characterize wave propagation in soft solids and a theoretical framework to understand how localized mechanical signals can provoke a remote and delayed response.

cond-mat.soft↗

Universal origin of boson peak vibrational anomalies in ordered crystals and in amorphous materials

The vibrational spectra of solids, both ordered and amorphous, in the low-energy regime, control the thermal and transport properties of materials, from heat capacity to heat conduction, electron-phonon couplings, conventional superconductivity etc. The old Debye model of vibrational spectra at low energy gives the vibrational density of states (VDOS) as proportional to the frequency squared, but in many materials the spectrum departs from this law which results in a peak upon normalizing the VDOS by frequency squared, which is known as the "boson peak". A description of the VDOS of solids (both crystals and glasses) is presented starting from first principles. Without using any assumptions whatsoever about the existence and nature of "disorder" in the material, it is shown that the boson peak in the VDOS of both ordered crystals and glasses arises naturally from the competition between elastic mode propagation and viscous damping. The theory explains the recent experimental observations of boson peak in perfectly ordered crystals, which cannot be explained based on previous theoretical frameworks. The theory also explains, for the first time, how the vibrational spectrum changes with the atomic density of the solid, and explains recent experimental observations of this effect.

cond-mat.soft↗