Ranko Richert

Dynamics of glass-forming liquids. V. On the link between molecular dynamics and configurational entropy

We compare dielectric relaxation τ(T) data of several low molecular weight glass-forming liquids with the predictions of the Adam–Gibbs theory using experimental data for the configurational entropy Sc(T). Combination of Adam–Gibbs and Vogel–Fulcher equations yields an expression for Sc(T) which can be compared with experimental data. Good agreement is found for a range of temperatures near Tg<T<TB which depends on the fragility of the liquid and on the presence of a β relaxation. For fragile liquids, TB coincides with a qualitative change in the temperature dependence of the relaxation time scale or viscosity, with the temperature Tβ, where Johari–Goldstein-type β processes tend to merge into the α process, and with other crossover temperatures. For nonfragile liquids, TB/Tg increases, and the deviations from the Adam–Gibbs equation weaken or disappear altogether. The significance of TB, and of the Sc(T) temperature dependence implied by the Vogel–Fulcher theory fitting, are discussed in terms of the lan...

Heterogeneous dynamics in liquids: fluctuations in space and time

The disordered nature of glass-forming melts gives rise to non-Arrhenius and non-exponential behaviour of their dynamics. With respect to the microscopic details involved in the structural relaxation, these materials have remained an unsolved puzzle for over a century. The observation of spatial heterogeneity regarding the dynamics provides an important step towards understanding the relation between the macroscopic properties of soft condensed matter and the molecular mechanisms involved. On the other hand, dynamic heterogeneity is the source of several new questions: What is the length scale and persistence time associated with such clusters of relaxation time? What is the signature of heterogeneity at high temperatures and in the glassy state? How do these features depend on the particular material and on the correlation function used for probing these heterogeneities? This work attempts to review the various approaches to heterogeneous dynamics and the generally accepted results, as well as some controversial issues. Undoubtedly, heterogeneity has provoked a number of novel experimental techniques targeted at studying glass-forming liquids at the molecular level. It will be emphasized that the picture of heterogeneity is a requirement for rationalizing an increasing number of experimental observations rather than just an alternative model for the dynamics of molecules.

DYNAMICS OF GLASS-FORMING LIQUIDS. I: TEMPERATURE-DERIVATIVE ANALYSIS OF DIELECTRIC RELAXATION DATA

We have measured the dielectric relaxation times of the α process of phenyl salicylate (salol) covering 11 decades in frequency. Being representative for the class of low molecular weight organic glass forming materials, the highly resolved temperature dependence of the dynamics in salol does not follow a particular function like the Vogel–Fulcher–Tammann (VFT) law over the entire accessible range of temperatures. In order to conduct a detailed and unambiguous analysis of the temperature dependence, we take advantage of the derivatives of the experimental log(fmax) values with respect to temperature, which allow us to either linearize the frequently used temperature laws or to resolve subtle changes in fmax(T) by decreasing the number of free parameters. In this manner we observe that none of the common routes for rationalizing the dynamics like Arrhenius, VFT, Souletie scaling, and idealized mode‐coupling theory account for the experimental findings properly. However, we do observe a VFT behavior within ...

Dynamics of glass‐forming liquids. II. Detailed comparison of dielectric relaxation, dc‐conductivity, and viscosity data

We have studied the temperature dependence of dielectric relaxation times in terms of the peak frequency fmax(T) of dielectric loss e″(ω) and the dc‐conductivity σdc(T) of several glass‐forming liquids, covering 12 decades in the peak frequency fmax and 9 decades in σdc. Although dc‐conductivity samples the mobility of ionic tracers, its variation with temperature is similar to that of fmax(T). The fmax(T) and σdc(T) are analyzed using the temperature‐derivative method and compared to the viscosity data η−1(T). While most liquids reveal a common Vogel–Fulcher–Tammann (VFT) behavior for fmax, σdc and η−1 in an extended temperature range T≥Tm, some liquids deviate from this behavior by displaying a crossover at T=TA to an Arrhenius regime. In these cases the quantity fmax(T) decouples from the common curves for σdc(T) and η−1(T) and attains activation energies in excess (∼40% for alcohols) of those related to translational processes. For many samples a departure from the VFT behavior occurs at lower tempera...

Dynamics of glass-forming liquids. III. Comparing the dielectric α- and β-relaxation of 1-propanol and o-terphenyl

We have measured the dielectric relaxation of the glass-former 1-propanol for temperatures between 65 and 350 K in the frequency range 10−2 to 2⋅1010 Hz and the photon correlation spectro-scopy decays near Tg. Attributing the strong Debye-type process of 1-propanol to distinct -OH group effects leaves two faster processes related to the structural relaxation which can be identified as α-relaxation and Johari–Goldstein type β-relaxation characteristic of nonhydrogen-bonding supercooled liquids. From the temperature dependent relaxation times τ(T) regarding the three distinct loss peaks, we can specify an α-β-bifurcation temperature Tβ, which coincides with characteristic qualitative changes in the τ(T) behavior, as also observed for ortho-terphenyl and other glass-forming liquids. This assignment is confirmed by the correla-tion times derived from incoherent quasielastic light-scattering data obtained from the simultaneously measured photon-correlation spectroscopy.

Fragility and thermodynamics in nonpolymeric glass-forming liquids

For nonpolymeric supercooled liquids, the empirical correlation m = 56Tg DeltaCp(Tg)/DeltaHm provides a reliable means of correlating dynamic and thermodynamic variables. The dynamics are characterized by the fragility or steepness index m and the glass transition temperature Tg, while thermodynamics enter in terms of the heat capacity step DeltaCp at Tg and the melting enthalpy DeltaHm. The combination of the above correlation with the 23 rule for the Tg/Tm ratio yields an expression, m = 40DeltaCp(Tg)/DeltaSm, which was rationalized as the correlation of the thermodynamic and kinetic fragilities. Defining a thermodynamic fragility via DeltaCp(Tg)/DeltaSm also reveals that the slopes in Kauzmanns original DeltaS(T)/DeltaSm versus T/Tm plot reflect the fragility concept [Chem. Rev. 43, 219 (1948)], so long as Tm/Tg = 1.5. For the many liquids whose excess heat capacity is a hyperbolic function of temperature, we deduce that the fragility cannot exceed m = 170, unless the Tg/Tm = 2/3 rule breaks down.

Hole transport in 1,1-bis(di-4-tolylaminophenyl)cyclohexane

Hole mobilities have been measured in vapor deposited films of 1,1‐bis(di‐4‐tolylaminophenyl)cyclohexane over an extended range of fields and temperatures. At 295 K, the mobility is approximately 10−2 cm2/V s, the highest value for a disordered molecular solid reported thus far. Monte Carlo simulations of random walk in a geometrically and energetically disordered medium demonstrate that the time dependence of the photocurrent and the field and temperature dependencies of the mobility can be described quantitatively in terms of the inherent disorder and its effect on charge transport. No polaronic or trapping phenomena need to be invoked to reproduce even subtle features of the experimental results.

Dynamics of hydrogen‐bonded liquids confined to mesopores: A dielectric and neutron spectroscopy study

In this paper we present and discuss experimental results on molecular mobility in propylene glycol and its three oligomers confined to the ∼100 A pores of a controlled porous glass. The objective is to elucidate the finite size effects on the dynamics of hydrogen‐bonded liquids of different molecular weights but identical chemical composition. The methods of dielectric and neutron spectroscopy have been employed to investigate both the low‐ and high‐frequency features as a function of temperature. We find that all fluids in pores separate into two distinct liquid phases. (i) molecules physisorbed at the surface which exhibit a dramatic frustration of their mobility related to a substantial positive shift of the glass transition temperature Tg by up to ΔTg≊+47 K; and (ii) relatively ‘‘free’’ molecules in the inner pore space subject to only moderate retardation of the α and normal mode relaxation and substantial broadening of the distribution of relaxation times. The shift in Tg for the α process with ΔTg...

Poole-Frenkel behavior of charge transport in organic solids with off-diagonal disorder studied by Monte Carlo simulation

Abstract By use of Monte Carlo simulation techniques it has been shown that inclusion of random variations of the wavefunction overlap parameter (‘off-diagonal’ disorder) generates Poole-Frenkel behavior of the charge-carrier mobility (μ) in random organic solids within an experimentally relevant range. The results are in quantitative agreement with experimental data, notably the work of Peled and Schein ( Chem. Phys. Lett., 153 (1988) 422) reporting on a temperature-induced change of sign of the field dependence of μ.

Dynamics of Nanoconfined Supercooled Liquids

Near their glass transition temperature T(g), supercooled liquids display dramatic changes regarding the dynamics if subject to geometrical restrictions on the scale of 2 to 200 nm. Confinement-induced shifts of T(g) of 25 K have been reported, equivalent to relaxation times that differ by several orders of magnitude compared with the bulk liquid at the same temperature. Both acceleration and frustration of structural relaxations have been observed, and the effects can depend strongly on the physical and chemical properties of the interface, on soft versus hard confinement, and on the size and dimensionality of the confining topology. This review attempts to extract a unifying picture from the past 20 years of diverse observations that involve experiments, simulations, and model considerations.