arXiv subjects
Publications and source records attributed to U. Buchenau.
The rapid structural and vibrational entropy decrease with decreasing temperature in undercooled liquids is explained in terms of the disappearance of local structural instabilities, which freeze in at the glass temperature as boson peak modes and low temperature tunneling states. At the Kauzmann temperature, their density extrapolates to zero, as evidenced by neutron and heat capacity data in liquid selenium.
The paper presents a description of the sound wave absorption in glasses, from the lowest temperatures up to the glass transition, in terms of three compatible phenomenological models. Resonant tunneling, the rise of the relaxational tunneling to the tunneling plateau and the crossover to classical relaxation are universal features of glasses and are well described by the tunneling model and its extension to include soft vibrations and low barrier relaxations, the soft potential model. Its further extension to non-universal features at higher temperatures is the very flexible Gilroy-Phillips model, which allows to determine the barrier density of the energy landscape of the specific glass from the frequency and temperature dependence of the sound wave absorption in the classical relaxation domain. To apply it properly at elevated temperatures, one needs its formulation in terms of the shear compliance. As one approaches the glass transition, universality sets in again with an exponential rise of the barrier density reflecting the frozen fast Kohlrausch t^beta-tail (in time t, with beta close to 1/2) of the viscous flow at the glass temperature. The validity of the scheme is checked for literature data of several glasses and polymers with and without secondary relaxation peaks. The frozen Kohlrausch tail of the mechanical relaxation shows no indication of the strongly temperature-dependent barrier density observed in dielectric data of molecular glasses with hydrogen bonds. Instead, the mechanical relaxation data indicate an energy landscape describable with a frozen temperature-independent barrier density for any glass.
The shear misfit model for the highly viscous flow is based upon a theoretical prediction for its terminal stage in terms of irreversible Eshelby relaxations in the five-dimensional shear space. The model is shown to predict a small delta-function (Debye peak) in the dielectric spectrum, in agreement with experimental evidence. It is extended from shear fluctuations to density fluctuations, a new relation between adiabatic and isothermal compressibility jumps at the glass transition is derived, and the model is brought into a form which requires only three temperature-dependent parameters for the fit of shear relaxation data of a glass former with a secondary relaxation peak. The model is applied to high precision measurements of the shear, dielectric and bulk relaxation data in two vacuum pump oils and in squalane, a short chain polymer with a strong secondary relaxation peak. In all three substances, the adiabatic compressibility equilibrates much earlier than the isothermal one. The terminal stage of aging data in squalane demonstrate that one sees also the adiabatic density fluctuations in the thermal expansion, explaining why it seems to equilibrate a bit faster than the dynamic heat capacity.
The glass transition in hydrogen-bonded glass formers differs from the glass transition in other glass formers. The Eshelby rearrangements of the highly viscous flow are superimposed by strongly asymmetric hydrogen bond rupture processes, responsible for the excess wing. Their influence on the shear relaxation spectrum is strong in glycerol and close to zero in PPE, reflecting the strength of the hydrogen bond contribution to the high frequency shear modulus. A recent theory of the highly viscous flow enables a quantitative common description of the relaxation spectra in shear, linear and non-linear dielectrics, and heat capacity.
The strain field surrounding the center of low frequency vibrational modes is analyzed for numerically created binary glasses with a 1/r^10 repulsive interatomic potential. Outside the unstable inner core of five to twenty atoms, one finds a mixture of a motion similar to the string motion in the core with the strain field of three oscillating elastic dipoles in the center. The additional outside string motion contributes more to the stabilization of the core than the strain field, but the strain field dominates at long distances, in agreement with recent numerical findings. The small restoring force of the outside string motion places its average frequency close to the boson peak. The average creation energy of a soft mode in this binary glass is about 2.5 times the thermal energy at the freezing temperature. Scaling the soft potential parameters of the numerical modes to metallic glasses, one finds quantitative agreement with measurements of the sound absorption by tunneling states at low temperatures and by the excess modes at the boson peak.
The recent theoretical treatment of irreversible jumps between inherent states with a constant density in shear space is extended to a full theory, attributing the shear relaxation to structural Eshelby rearrangements involving the creation and annihilation of soft modes. The scheme explains the Kohlrausch exponent close to 1/2 and the connection to the low temperature glass anomalies. A continuity relation between the irreversible and the reversible Kohlrausch relaxation time distribution is derived. The full spectrum can be used in many ways, not only to describe shear relaxation data, but also to relate shear relaxation data to dielectric and bulk relaxation spectra, and to predict aging from shear relaxation data, as demonstrated for a very recent aging experiment.
The anharmonic soft modes studied in recent numerical work in the glass phase of simple liquids have an unstable core, stabilized by the positive restoring forces of the surrounding elastic medium. The present paper formulates an unstable core version of the phenomenological soft potential model for the low temperature anomalies of glasses, relates a new numerical finding on low-barrier relaxations to old soft potential model results, and discusses experimental evidence for an unstable core of the boson peak modes.
Inelastic neutron scattering is not only capable of determining a generalized vibrational density of states around the boson peak of a glass, but can also be used to get information on the eigenvectors. The eigenvectors determine the dynamic structure factor, which is $Q^2S(Q)$ ($Q$ wavevector) for long wavelength sound waves. This enables the determination of the sound wave fraction below and at the boson peak, done for SiO$_2$, B$_2$O$_3$, polybutadiene and amorphous germanium. The temperature dependence of the boson peak in silica and glycerol is shown. X-ray Brillouin scattering data show that the damping of the longitudinal sound waves in silica and glycerol follows the soft potential model $ω^4$ prediction in the limit of low frequency.
Supplemental Material to ArXiv:1902.02746
The recent description of the cooling through the glass transition in terms of irreversible structural Eshelby rearrangements with a single average fictive temperature is extended to a distribution of fictive temperatures around the average one. The extension has only little influence on the cooling scans, but turns out to be necessary to understand the heating back to equilibrium.
The recent description of the highly viscous flow in terms of irreversible structural Eshelby rearrangements is extended to calculate the heat capacity of a glass former at a constant cooling rate through the glass transition. The result is compared to measured data from the literature, showing that the explanation works both for polymers and other glass formers.
The recent Eshelby description of the highly viscous flow leads to the prediction of a factor of two different viscosities in stationary and alternating flow, in agreement with experimental evidence. The Kohlrausch barrier density increase with increasing barrier height finds a physical justification in the Adam-Gibbs increase of the number of structural alternatives of the Eshelby region with its increasing size. The new Ansatz allows to determine the number of atoms or molecules in the rearranging Eshelby domains from a combination of dynamic shear relaxation and calorimetric data.
A recent description of the highly viscous flow ascribes it to irreversible thermally activated Eshelby transitions, which transform a region of the undercooled liquid to a different structure with a different elastic misfit to the viscoelastic surroundings. The description is extended to include reversible Eshelby transitions, with the Kohlrausch exponent $β$ as a free parameter. The model answers several open questions in the field.
The highly viscous flow is due to thermally activated Eshelby transitions which transform a region of the undercooled liquid to a different structure with a different elastic misfit to the viscoelastic surroundings. A self-consistent determination of the viscosity in this picture explains why the average structural relaxation time is a factor of eight longer than the Maxwell time. The physical reason for the short Maxwell time is the very large contribution of strongly strained inherent states to the fluidity (the inverse viscosity). At the Maxwell time, the viscous no-return processes coexist with the back-and-forth jumping retardation processes.
The paper derives a relation for the viscosity of undercooled liquids on the basis of the pragmatical model concept of Eshelby relaxations with a finite lifetime. From accurate shear relaxation data in the literature, one finds that slightly less than half of the internal stresses relax directly via single Eshelby relaxations; the larger part dissolves at the terminal lifetime, which is a combined effect of many Eshelby relaxations.
The recently developed pragmatical model of asymmetric double-well potentials with a finite lifetime is applied to nonlinear dielectric data in polar undercooled liquids. The viscous effects from the finite lifetime provide a crossover from the cooperative jumps of many molecules at short times to the motion of statistically independent molecules at long times. The model allows to determine the size of cooperatively rearranging regions from nonlinear ω-data and throws a new light on a known inconsistency between nonlinear ω and 3ω-signals for glycerol and propylene carbonate.
The Grüneisen relation is shown to be important for the thermodynamics of dense liquids.
According to a recent numerical finding, the dynamics of a glass former is exclusively due to the forces within the first coordination shell. This implies that the Kohlrausch beta should be understandable in terms of the effective nearest-neighbor potential. The present paper proposes a relation for the Kohlrausch beta based on the Adam-Gibbs conjecture of a flow barrier proportional to the number of atoms or molecules in a cooperatively rearranging region. The conjecture implies that beta is given by the ratio of the structural entropy increase per particle to the barrier increase per particle. Making use of a recent numerical determination of the structural entropy per particle in Lennard-Jones-like potentials, one can show that the relation leads to values between 0.3 and 0.6.