ESR evidence of the dynamic crossover in the supercooled liquid states of a series of solid n-alkanes.

A study of the rotation dynamics of the spin probe TEMPO by electron spin resonance (ESR) spectroscopy in a series of six short- and medium-sized n-alkanes is presented. In addition to the usual crossover effects connected with solid-liquid phase transitions at temperature Tm and the solid-solid transition at Tss, we find a strong correlation between the change in reorientation at the characteristic ESR temperature TfastX1 < Tss and/or Tm with the ratio TfastX1/Tm = 0.76 ± 0.03 and the characteristic dynamic temperature, TX, obtained from the viscosity data. This indicates the presence of local disordered regions in the crystalline structure which is indeed sensitive to dynamic change at the crossover temperature TX ≅ TfastX1.

Primary α and secondary ß relaxation dynamics of meta-toluidine in the liquid state investigated by broadband dielectric spectroscopy.

We report a broadband dielectric spectroscopic (BDS) study on the clustering fragile glass-former meta-toluidine (m-TOL) from 187 K up to 289 K over a wide frequency range of 10-3-109 Hz with focus on the primary α relaxation and the secondary ß relaxation above the glass temperature Tg. The broadband dielectric spectra were fitted by using the Havriliak-Negami (HN) and Cole-Cole (CC) models. The ß process disappearing at Tß,disap = 1.12Tg exhibits non-Arrhenius dependence fitted by the Vogel-Fulcher-Tamman-Hesse equation with T0ßVFTH in accord with the characteristic differential scanning calorimetry (DSC) limiting temperature of the glassy state. The essential feature of the α process consists in the distinct changes of its spectral shape parameter ßHN marked by the characteristic BDS temperatures TB1ßHN and TB2ßHN. The primary α relaxation times were fitted over the entire temperature and frequency range by several current three-parameter up to six-parameter dynamic models. This analysis reveals that the crossover temperatures of the idealized mode coupling theory model (TcMCT), the extended free volume model (T0EFV), and the two-order parameter (TOP) model (Tmc) are close to TB1ßHN, which provides a consistent physical rationalization for the first change of the shape parameter. In addition, the other two characteristic TOP temperatures T0TOP and TA are coinciding with the thermodynamic Kauzmann temperature TK and the second change of the shape parameter at around TB2ßHN, respectively. These can be related to the onset of the liquid-like domains in the glassy state or the disappearance of the solid-like domains in the normal liquid state.

Molecular dynamic heterogeneity in relation to free volume and relaxation dynamics in organic glass-formers: oligomeric cis-1,4-poly(isoprene).

Herein, a combined study of the molecular rotation dynamics and free volume in cis-1,4-poly(isoprene) using two external probing techniques via ESR and PALS together with relaxation dynamics of the host medium via BDS is presented. The spectral evolution of the spin probe TEMPO from simulations over a wide range from 100 K up to 300 K exhibits three different regions of its correlation time consisting of a slow regime at low temperatures followed by the molecular dynamic heterogeneity zone from T = T = 155 K = 0.82 × T up to Tc ≅ 236 K = 1.26 × T and ending with a fast regime at high temperatures with the further characteristic ESR temperatures, T = 186 K ≅ T and T = 260 K. These are in close coincidence with four characteristic PALS temperatures: T = 160 K, T = 190 K, T = 227 K, and T = 263 K. Finally, using BDS, we revealed that the high-frequency features of the structural relaxation of 1,4-PIP 0.8k were related to the observed effects in the ESR and PALS response of the liquid state.

Molecular probe dynamics and free volume in organic glass-formers and their relationships to structural relaxation: 1-propanol.

A joint study of the rotational dynamics and free volume in amorphous 1-propanol (1-PrOH) as a prototypical monohydroxy alcohol by electron spin resonance (ESR) or positron annihilation lifetime spectroscopy (PALS), respectively, is reported. The dynamic parameters of the molecular spin probe 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and the annihilation ones of the atomic ortho-positronium (o-Ps) probe as a function of temperature are compared. A number of coincidences between various effects in the ESR and PALS responses at the corresponding characteristic ESR and PALS temperatures were found suggesting a common origin of the underlying dynamic processes that were identified using viscosity (VISC) in terms of the two-order parameter (TOP) model and broadband dielectric spectroscopy (BDS) data.

Positron annihilation and relaxation dynamics from dielectric spectroscopy: poly(vinylmethylether).

We report on the temperature dependence of the lifetime of the ortho-positronium (o-Ps), τ(3), annihilation in amorphous polymer poly(vinylmethylether) (PVME) from positron annihilation lifetime spectroscopy (PALS). We show that the behavior of τ(3)(T) can be divided into five regions, each of them having a linear temperature dependence, and that the crossover PALS temperatures situated at T(b1)(G), 0.76T(g)(PALS), T(b1)(L) = 1.14T(g)(PALS) and T(b2)(L) = 1.37T(G)(PALS), and marking the discontinuity in the free volume microstructure are related to various dynamic features from neutron scattering (NS) and broadband dielectric spectroscopy (BDS). First, a slight change in the PALS response in the glassy PVME at T(b1)(G) is related to the onset of the excess wing in an apparent correspondence with the fast secondary ß motion from NS. A further slight bend in the liquid state at T(b1)(L) is related to a high-frequency tail of the primary α process as well as to the slow secondary ß relaxation from BDS. In addition, it lies also in the vicinity of the crossover temperature, T(B)(ßKWW), in the spectral dispersion of the primary α process, indicating a connection of the change in the o-Ps lifetime with the variation in the width of the primary α relaxation times distribution. Finally, the τ(3) value at T(b2)(L) is close to the mean relaxation time of the primary α process, τ(α), in coincidence with the crossover in the secondary effective ß process between two regimes in the liquid PVME. All these relationships point to very close connections between the PALS response and the dynamic behavior of PVME, which can be explained in terms of the temperature dependence of the probability function of the liquid-like and the solid-like domains, as obtained from the two-order parameter (TOP) model description of the liquid to glass transition in glass-formers.