Coarsening in a driven Ising chain with conserved dynamics

We study the low-temperature coarsening of an Ising chain subject to spin-exchange dynamics and a small driving force. This dynamical system reduces to a domain diffusion process, in which entire domains undergo nearest-neighbor hopping, except for the shortest domains-dimers-which undergo long-range hopping. This system exhibits anomalous ordering dynamics due to the existence of two characteristic length scales: the average domain length L(t) approximately t(1/2) and the average dimer hopping distance l(t) approximately square root[L(t)] approximately t(1/4). As a consequence of these two scales, the density of short domains decays as t(-5/4), instead of the t(-3/2) decay that would arise from pure domain diffusion.     

Polaron spin-lattice relaxation time in pi-conjugated polymers from optically detected magnetic resonance

We describe a method for obtaining the polaron spin-lattice relaxation time T{SL} in pi-conjugated polymers by measuring the optically detected magnetic resonance (ODMR) dynamics as a function of microwave power and laser intensity. The peculiar ODMR dynamics is well described by a spin dependent recombination model where both recombination and spin relaxation rates determine together the response dynamics. We apply this method to the spin 1/2 ODMR in films of pristine 2-methoxy-5-(2{'}-ethylhexyloxy) phenylene vinylene [MEH-PPV] polymer, as well as MEH-PPV doped with various concentrations of radical impurities. We obtained T{SL} approximately 30 micros in pristine MEH-PPV, but substantially shorter when the magnetic impurities are added.     

Probing slow dynamics in supported thin polymer films

We have used variable cooling rate ellipsometric measurements to probe the slow dynamics in thin supported polystyrene films. For the slowest cooling rates (approximately 1 K/min) the measured Tg values are reduced below the bulk value with the measured Tg of 341 K for a 6 nm film. As the cooling rate is increased the Tg reductions become smaller until at cooling rates >90 K/min there is only slight evidence for a film-thickness-dependent Tg value. By relating the cooling rate to a relaxation time, we show that the relaxation dynamics of the thin films appears to become Arrhenius with an activation energy that decreases with decreasing film thickness. We discuss this in terms of a possible connection to a length scale for cooperative motion. Finally, the results can be used to resolve a number of outstanding contradictory reports in the literature.     

From a simple liquid to a polymer melt: NMR relaxometry study of polybutadiene

We utilize NMR field cycling relaxometry to study the crossover from glassy dynamics (t approximately > tau alpha) through Rouse to reptation behavior in a series of monodisperse polybutadienes with molecular weights M=355 to 817,000 g/mol. We separate characteristic polymer dynamics from the total spectrum dominated by glassy dynamics. The polymer dynamics show typical Rouse relaxation features that grow with M and saturate at high M. Comparing to Rouse theory, we determine the Rouse unit size MR approximately = 500 and entanglement weight Me approximately = 2000; the Rouse spectrum saturates at Mmax approximately = 4000. The local order parameter S approximately 0.11 is relatively large, indicating noticeable local packing already in the Rouse regime. The M dependence of the glass transition temperature Tg, obtained from dielectric relaxation spectra, shows distinctive kinks at MR and Me.     

Rotational dynamics and friction in double-walled carbon nanotubes

We report a study of the rotational dynamics in double-walled nanotubes using molecular dynamics simulations and a simple analytical model that reproduces the observations very well. We show that the dynamic friction is linear in the angular velocity for a wide range of values. The molecular dynamics simulations show that for large enough systems the relaxation time takes a constant value depending only on the interlayer spacing and temperature. Moreover, the friction force increases linearly with contact area and the relaxation time decreases with the temperature with a power law of exponent -1.53+/-0.04.     

Nonlinear losses in photoconductive Yb:YAG laser materials: identification of photocarrier properties by non-steady-state photoEMF

We report on the investigation of the photocarrier sign and the excitation dynamics in Yb:YAG at 940 nm excitation wavelength by non-steady-state photo-electromotive force technique. Annealed crystals with 25 and 50 % Yb-doping concentration demonstrate hole conductivity, while 80 % Yb:YAG displays electron conductivity. A characteristic relaxation time of approximately 1 ms is observed, which corresponds to the lifetime of the excited Yb³⁺-ion.     

Longitudinal relaxation of initially straight flexible and stiff polymers

The relaxation mechanism of an initially straight flexible or stiff polymer chain of length N in a viscous solvent is studied through Brownian dynamics simulations covering a broad range of time scales. After the short-time free diffusion, the chain's longitudinal reduction R2(0)-R2 approximately Nt1/2 at early intermediate times is shown to constitute a universal behavior for any chain stiffness caused by a quasisteady T approximately Nt(-1/2) relaxation of tensions associated with the deforming action of the Brownian forces. Stiff chains with a persistence length E > or = N are shown to exhibit a late intermediate-time longitudinal reduction R2(0)-R2 approximately N2E(-3/4)t1/4 associated with a T approximately N2E(-3/4)t(-3/4) relaxation of tensions affected by the deforming Brownian and the restoring bending forces.     

Nonlinear viscoelastic dynamics of nanoconfined wetting liquids

The viscoelastic dynamics of nanoconfined wetting liquids is studied by means of atomic force microscopy. We observe a nonlinear viscoelastic behavior remarkably similar to that widely observed in metastable complex fluids. We show that the origin of the measured nonlinear viscoelasticity in nanoconfined water and silicon oil is a strain rate dependent relaxation time and slow dynamics. By measuring the viscoelastic modulus at different frequencies and strains, we find that the intrinsic relaxation time of nanoconfined water is in the range 0.1-0.0001 s, orders of magnitude longer than that of bulk water, and comparable to the dielectric relaxation time measured in supercooled water at 170-210 K.     

Substrate and chain size dependence of near surface dynamics of glassy polymers

We use nanohole relaxation to study the surface relaxation of films of glassy isotactic poly (methyl methacrylate) (i-PMMA) films. These measurements allow us to obtain the time dependent relaxation function at a number of different sample temperatures for the first 2-3 nm of the free surface in a system often used as a model system for the effect of the substrate on thin film dynamics. The surface is observed to relax at temperatures up to 42 K below the bulk Tg value, even on systems where the thin film Tg is known to be greater than the bulk value. We are able to determine the range over which the substrate directly affects the free surface relaxation, and determine a surprisingly large (Mw independent) limiting thickness of approximately 180 nm where the free surface relaxation is not affected by the substrate. For thick films (h>200 nm) we find an unexpected linear Mw dependence of the near surface relaxation time.     

The polymer mat: arrested rebound of a compressed polymer layer

Compression of an adsorbed polymer layer distorts its relaxed structure. Surface force measurements from different laboratories show that the return to this relaxed structure after the compression is released can require tens of minutes and that the recovery time can grow rapidly with molecular weight. We argue that the arrested state of the free layer before relaxation can be described as a Guiselin brush structure (O. Guiselin, Europhys. Lett. 17, 225 (1992)), in which the monomer density falls off only weakly with distance from the surface. This brush structure predicts an exponential falloff of the force at large distance with a decay length that varies as the initial compression distance to the 6/5 power. This exponential falloff is consistent with surface force measurements. We propose a relaxation mechanism that accounts for the increase in relaxation time with chain length.     

Ultrafast quenching of ferromagnetism in InMnAs induced by intense laser irradiation

Time-resolved magneto-optical Kerr spectroscopy of ferromagnetic InMnAs reveals two distinct demagnetization processes--fast (<1 ps) and slow (approximately 100 ps). Both components diminish with increasing temperature and are absent above the Curie temperature. The fast component rapidly grows with pump power and saturates at high fluences (>10 mJ/cm(2)); the saturation value indicates a complete quenching of ferromagnetism on a subpicosecond time scale. We attribute this fast dynamics to spin heating through p-d exchange interaction between photocarriers and Mn ions, while the approximately 100 ps component is interpreted as spin-lattice relaxation.     

Dynamics of driven Brownian inverted oscillator

In this paper, we derive the quantum Langevin equation for a driven Brownian inverted oscillator in the framework of the Heisenberg picture for the Caldeira-Leggett model. We describe the influence of an arbitrary time-dependent force on an open inverted oscillator dynamics. We take into account environment through the integral operator of relaxation and the force correlation function. The resulting behavior of the system is represented as a combination the time evolution of the position expectation and the variance, being induced simultaneously by spreading the wave packet and the chaotic Brownian motion. We discuss the possibility of stabilization of an open inverted oscillator, when applying external alternating force.     

Effective temperature scaled dynamics of a flexible polymer in an active bath

Langevin dynamics simulations are employed to study the dynamical properties of a flexible polymer in an active bath. The diffusion of the centre of mass and end-to-end distance fluctuation are particularly analysed. We modulate both active force and active particle size to probe the activity-induced facilitation of polymer dynamics. Results indicate diffusivity and chain relaxation time can be well scaled by the effective temperature of the active bath. In addition, diffusion dynamics demonstrates an anomalous superdiffusive behaviour in short time scales, which becomes more prominent with increasing active particle size. Lastly, we extract the effective viscosity experienced by the probed chain, showing a sharp decrease with increment of effective temperature. The attenuation of effective viscosity due to activity might be responsible for the facilitated polymer dynamics.     

Structure and dynamics of water confined in silica hydrogels: X-ray scattering and dielectric spectroscopy studies

We have used a sol-gel technique to obtain optically transparent hydrogels in which water is confined within a 3D silica matrix. In this work we report X-ray scattering and dielectric spectroscopy measurements on samples having different aging times and compare them with previously obtained results with near-infrared (NIR) absorption spectroscopy. X-ray scattering at room temperature enables to characterize the structure and size of the matrix pores and the non-uniform distribution of water inside the hydrogel. Broad band dielectric spectroscopy in the temperature range 130-280 K enables to study water dynamics. In aged hydrogels two relaxations are clearly evident and show characteristic temperature dependence. The faster relaxation has an Arrhenius behavior in the whole temperature range investigated with an activation enthalpy of approximately 50 kJ/mol; it is attributed to water molecules strongly interacting with the silica matrix. The slower relaxation has a markedly non-Arrhenius behavior which can be fitted with a Vogel-Fulcher-Tamman (VFT) relation with critical temperature of approximately 100 K and activation enthalpies of 35 and 95 kJ/mol at 300 and 170 K respectively; it is attributed to water molecules within the pores that do not interact strongly with the matrix and behave collectively. The VFT temperature dependence of the dielectric relaxation time suggests that this water does not crystallize, in agreement with previous results from NIR spectroscopy.     

Evolution of particle-scale dynamics in an aging clay suspension

Multispeckle x-ray photon correlation spectroscopy was employed to characterize the slow dynamics of a suspension of highly charged, nanometer-sized disks. At wave vectors q corresponding to interparticle length scales, the dynamic structure factor follows a form f(q,t) approximately exp([-(t/tau)(beta)], where beta approximately 1.5. The relaxation time tau increases with the sample age t(a) approximately as tau approximately t(1.8)(a) and decreases with q as tau approximately q(-1). Such behavior is consistent with models that describe the dynamics in disordered elastic media in terms of strain from random, local structural rearrangements. The measured amplitude of f(q,t) varies with q in a manner that implies caged particle motion. The decrease in the range of this motion and an increase in suspension conductivity with increasing t(a) indicate a growth in interparticle repulsion as the mechanism for internal stress development implied by these models.     

Domain shape relaxation and local viscosity in stratifying foam films

We studied the dynamics of two different types of domain shape relaxation in a stratifying foam film composed of an anionic polymer and cationic surfactant. Those films thin in stepwise fashion: circular domains of lower film thickness are formed, expand and coalesce until they cover the whole film surface. We found that the shape relaxation of coalescing domains is governed only by 2D dissipation, and the measurement of the time scales allows to determine the ratio between the driving force (line tension) and local film viscosity. Further, we analyzed the withdrawal of stripes and modeled it by a moving disc pulled by an external force. Here, 3D dissipation can not be neglected (Stokes paradox) and the equilibrium velocity depends logarithmically on the viscosity of the surrounding 3D air. The evaluation of both kinds of relaxation events yields the orders of magnitude of film viscosity and line tension. For the investigated system we found that the film viscosity is at least 30 times larger than the bulk viscosity, which can be explained by the local molecular ordering and strong interactions with film surfaces.     

Analysis of inelastic x-ray scattering spectra of low-temperature water

We analyze a set of high-resolution inelastic x-ray scattering (IXS) spectra from H2O measured at T=259, 273, and 294 K using two different phenomenological models. Model I, called the "dynamic cage model," combines the short time in-cage dynamics described by a generalized Enskog kinetic theory with a long-time cage relaxation dynamics described by an alpha relaxation. This model is appropriate for supercooled water where the cage effect is dominant and the existence of an alpha relaxation is evident from molecular-dynamics (MD) simulation data of extended simple point charge (SPC/E) model water. Model II is essentially a generalized hydrodynamic theory called the "three effective eigenmode theory" by de Schepper et al. 11. This model is appropriate for normal liquid water where the cage effect is less prominent and there is no evidence of the alpha relaxation from the MD data. We use the model I to analyze IXS data at T=259 K (supercooled water). We successfully extract the Debye-Waller factor, the cage relaxation time from the long-time dynamics, and the dispersion relation of high-frequency sound from the short time dynamics. We then use the model II to analyze IXS data at all three temperatures, from which we are able to extract the relaxation rate of the central mode and the damping of the sound mode as well as the dispersion relation for the high-frequency sound. It turns out that the dispersion relations extracted from the two models at their respective temperatures agree with each other giving the high-frequency sound speed of 2900+/-300 m/s. This is to be compared with a slightly higher value reported previously, 3200+/-320 m/s, by analyzing similar IXS data with a phenomenological-damped harmonic oscillator model 22. This latter model has traditionally been used exclusively for the analysis of inelastic scattering spectra of water. The k-dependent sound damping and central mode relaxation rate extracted from our model analyses are compared with the known values in the hydrodynamic limit.     

Computer simulation of nanoindentation into polymer films

We present computer simulations of nanoindentation into amorphous polymer films. The bulk polymer is treated through a united atom model in connection with molecular dynamics methods. The dynamics of the indenter is modeled as overdamped, such that the indentation velocity is proportional to the difference between the external force acting onto the tool and the resistance force built up in the polymer film. We concentrate on the initial, kinetic stage of the indentation process and give results for the motion of the indenter, the deformation field of the polymer film, the stress field, and the field of total monomer energy. We propose an effective coefficient as a new measure for the resistivity of a surface against indentation. Its value can be determined in an experiment with constant indentation velocity. In addition, we investigate the free drift behavior when the external driving force has been set to zero and the tool is expelled from the polymer film. For different polymer chain lengths, the tool’s motion is exponential in time and we determine the relaxation scale.     

UV isomerisation in nematic elastomers as a route to photo-mechanical transducer

The macroscopic shape of liquid-crystalline elastomers strongly depends on the order parameter of the mesogenic groups. This order can be manipulated if photo-isomerisable groups, e.g. containing N=N bonds, are introduced into the material. We have explored the large photo-mechanical response of such an azobenzene-containing nematic elastomer at different temperatures, using force and optical birefringence measurements, and focusing on fundamental aspects of population dynamics and the related speed and repeatability of the response. The characteristic time of "on" and "off" regimes strongly depends on temperature, but is generally found to be very long. We were able to verify that the macroscopic relaxation of the elastomer is determined by the nematic order dynamics and not, for instance, by the polymer network relaxation.     

Femtonewton force spectroscopy of single extended DNA molecules

We studied the thermal fluctuations of single DNA molecules with a novel optical tweezer based force spectroscopy technique. This technique combines femtonewton sensitivity with millisecond time resolution, surpassing the sensitivity of previous force measurements in aqueous solution with comparable bandwidth by a hundredfold. Our data resolve long-standing questions concerning internal hydrodynamics of the polymer and anisotropy in the molecular relaxation times and friction coefficients. The dynamics at high extension show interesting nonlinear behavior.