Static and dynamic properties of supercooled thin polymer films

The dynamic and static properties of a supercooled (non-entangled) polymer melt are investigated via molecular-dynamics (MD) simulations. The system is confined between two completely smooth and purely repulsive walls. The wall-to-wall separation (film thickness), D, is varied from about 3 to about 14 times the bulk radius of gyration. Despite the geometric confinement, the supercooled films exhibit many qualitative features which were also observed in the bulk and could be analyzed in terms of mode-coupling theory (MCT). Examples are the two-step relaxation of the incoherent intermediate scattering function, the time-temperature superposition property of the late time α-process and the space-time factorization of the scattering function on the intermediate time scale of the MCT β-process. An analysis of the temperature dependence of the α-relaxation time suggests that the critical temperature, T _c, of MCT decreases with D. If the confinement is not too strong ( D≥10monomer diameter), the static structure factor of the film coincides with that of the bulk when compared for the same distance, T - T _c(D), to the critical temperature. This suggests that T - T _c(D) is an important temperature scale of our model both in the bulk and in the films. Received 12 September 2001     

Investigation of a magnetic phase transition in fcc iron-nickel alloys

A magnetic phase transition in carbon-doped (0.1 and 0.7 at. %) Fe₇₀Ni₃₀ Invar alloys was investigated by the method of depolarization of a transmitted neutron beam and by small-angle scattering of polarized neutrons. It is shown that for both alloys, two characteristic length scales of magnetic correlations coexist above T _c. Small-angle scattering by critical correlations with radius R _c is described well by the Ornstein-Zernike (OZ) expression. The longer-scale (second) correlations, whose size can be estimated from depolarization data, are not described by the OZ expression, and hypothetically can be modeled by a squared OZ expression, which in coordinate space corresponds to the relation 〈M(r)M(0)〉∝exp(−r/R _d), where R _d is the correlation length of the second scale. The temperature dependence of the correlation radius R _c was obtained: R _c ∝ ((T−T _c)/Tc)^−ν , where ν≈2/3 is the critical exponent for ferromagnets, over a wide temperature range up to T _c ^exp , at which the correlation radius becomes constant and equals its maximum value R _c(T _c)=R _c ^max . The maximum correlation radius established (R _c ^max =140 Å and 230 Å for the first and second alloys, respectively) characterizes the length-scale of the fluctuation for which the appearance of critical correlations first results in the formation of a ferromagnetic phase, and the phenomenon itself exhibits a “disruption” of the second-order phase transition at T=T _c ^exp , as a result of which a first-order transition arises. Temperature hysteresis was also detected in the measured polarization of the transmitted beam and intensity of small-angle neutron scattering in the alloy above T _c, confirming the character of this magnetic transition as a first-order transition close to a second-order transition. Zh. éksp. Teor. Fiz. 112, 2134–2155 (December 1997)     

Globules of annealed amphiphilic copolymers: Surface structure and interactions

A mean-field theory of globules of random amphiphilic copolymers in selective solvents is developed for the case of an annealed copolymer sequence: each unit can be in one of two states, H (insoluble) or P (soluble or less insoluble). The study is focussed on the regime when H and P units tend to form long blocks, and when P units dominate in the dilute phase, but are rare in the globule core. A first-order coil-to-globule transition is predicted at some T = T _cg. The globule core density at the transition point increases as the affinity of P units to the solvent, ˜, is increased. Two collapse transitions, coil → “loose” globule and “loose” globule → “dense” globule, are predicted if ˜ is high enough and P units are marginally soluble or weakly insoluble. H and P concentration profiles near the globule surface are obtained and analyzed in detail. It is shown that the surface excess of P units rises as ˜ is increased. The surface tension decreases in parallel. Considering the interaction between close enough surfaces of two globules, we show that they always attract each other at a complete equilibrium. It is pointed out, however, that such equilibrium may be difficult to reach, so that partially equilibrium structures (defined by the condition that a chain forming one globule does not penetrate into the core of the other globule) are relevant. It is shown that at such partial equilibrium the interaction is repulsive, so the globules may be stabilized from aggregation. The strongest repulsion is predicted at the coil-to-globule transition point T _cg: the repulsion force decreases with the distance between the surfaces according to a power law. In the general case (apart from T _cg) the force vs. distance decay becomes exponential; the decay length ξ diverges as T → T _cg. The developed theory explains certain anomalous properties observed for globules of amphiphilic homopolymers.     

MD simulation of concentrated polymer solutions: Structural relaxation near the glass transition

We examine by molecular dynamics simulations the relaxation of polymer-solvent mixtures close to the glass transition. The simulations employ a coarse-grained model in which polymers are represented by bead-spring chains and solvent particles by monomers. The interaction parameters between polymer and solvent are adjusted such that mixing is favored. We find that the mixtures have one glass transition temperature T _g or critical temperature T _c of mode-coupling theory (MCT). Both T _g and T _c (> T _g decrease with increasing solvent concentration . The decrease is linear for the concentrations studied (up to = 25%. Above T _c we explore the structure and relaxation of the polymer-solvent mixtures on cooling. We find that, if the polymer solution is compared to the pure polymer melt at the same T, local spatial correlations on the length scale of the first peak of the static structure factor S(q) are reduced. This difference between melt and solution is largely removed when comparing the S(q) of both systems at similar distance to the respective T _c. Near T _c we investigate dynamic correlation functions, such as the incoherent intermediate scattering function (t), mean-square displacements of the monomers and solvent particles, two non-Gaussian parameters, and the probability distribution P(ln r;t) of the logarithm of single-particle displacements. In accordance with MCT we find, for instance, that (t) obeys the time-temperature superposition principle and has relaxation times which are compatible with a power law increase close (but not too close) to T _c. In divergence to MCT, however, the increase of depends on the wavelength q, small q values having weaker increase than large ones. This decoupling of local and large-length scale relaxation could be related to the emergence of dynamic heterogeneity at low T. In the time window of the relaxation an analysis of P(ln r;t) reveals a double-peak structure close to T _c. The first peak correponds to “slow” particles (monomer or solvent) which have not moved much farther than 10% of their diameter in time t, whereas the second occurs at distances of the order of the particle diameter. These “fast” particles have succeeded in leaving their nearest-neighbor cage in time t. The simulation thus demonstrates that large fluctuations in particle mobility accompany the final structural relaxation of the cold polymer solution in the vicinity of the extrapolated T _c.     

Potential ultra-incompressible material ReN: First-principles prediction

The structural, elastic and electronic properties of ReN are investigated by first-principles calculations based on density functional theory (DFT). The most stable structure of ReN is a NiAs-like structure, belonging to space group P6₃/mmc with a=2.7472 and c=5.8180 Å. ReN is a metallic ultra-incompressible solid and it exhibits low elastic anisotropy. Its linear incompressibility along the c-axis exceeds that of diamond. Its ultra-incompressibility is attributed to the high valence electron density and strong covalence bondings. Our results indicate that ReN can be used as a potential ultra-incompressible conductor. In particular, a superconducting transition temperature is predicted as T_c≈4.8 K for NiAs-like ReN, which agrees well with the available experimental value.     

A pseudopotential approach to the superconducting state parameters of (Ni33Zr67)1? x M x (M=Ti, V, Co, Cu) ternary metallic glasses

Superconductivity in ternary metallic glasses has been investigated using the model pseudopotential approach, which has been found quite successful in explaining superconductivity in metals, binary alloys and binary glasses. It is observed that this simple methodology successfully explains superconducting behaviour of ternary glasses without requiring the solution of Dirac equation for a many body problem or estimation of various interactions as required in ab-initio pseudopotential theory. In the present work superconducting state parameters of fourteen metallic glasses of (Ni-Zr)-M system (M=Ti, V, Co, Cu) have been determined in the BCS-Eliashberg-McMillan framework. It is observed that addition of V, Co, and Cu as the third element (M) to a binary metallic glass (Ni₃₃ Zr₆₇) causes the parameters λ,T _c, α, andN ₀ V to decrease, and Coulomb pseudopotential (μ*) to increase with concentration of M, showing that the presence of third element (M) causes suppression of superconducting behaviour of the alloy. The decrease inT _c with increasing concentration of third element (M) may be attributed to the modifications in density of states at the Fermi levelN(E _F), and probable changes in the band structure of the alloy due to addition of the third element (M). Slight difference is noticed when Ti is added to the Ni₃₃ Zr₆₇ alloy. In this caseT _c rises initially and then decreases with concentration of M, showing a peak at aboutx=0.05. This indicates that on addition of Ti, 3d states grow near the Fermi level and hence contribute substantially toN(E _F), favouring superconducting behaviour in this case. The present results forT _c show an excellent agreement with the experimental data. QuadraticT _c equations have been proposed, which provide successfully theT _c values of ternary metallic glasses under consideration. Paper presented at National Conference on Current Trends in Condensed Matter Research, Warangal, India, September 20–22, 2004.     

Temporal correlations and persistence in the kinetic Ising model: the role of temperature

We study the statistical properties of the sum S _t = dt'σ _t', that is the difference of time spent positive or negative by the spin σ _t, located at a given site of a D-dimensional Ising model evolving under Glauber dynamics from a random initial configuration. We investigate the distribution of S_t and the first-passage statistics (persistence) of this quantity. We discuss successively the three regimes of high temperature ( T > T _c), criticality ( T = T _c), and low temperature ( T < T _c). We discuss in particular the question of the temperature dependence of the persistence exponent , as well as that of the spectrum of exponents (x), in the low temperature phase. The probability that the temporal mean S _t/t was always larger than the equilibrium magnetization is found to decay as t ^{- - ?}. This yields a numerical determination of the persistence exponent in the whole low temperature phase, in two dimensions, and above the roughening transition, in the low-temperature phase of the three-dimensional Ising model. Received 4 December 2000     

Effective interactions and superconductivity in the t-J model in the large-N limit

The feasibility of a perturbation expansion for Green's functions of the t-J model directly in terms of X-operators is demonstrated using the Baym-Kadanoff functional method. As an application we derive explicit expressions for the kernel of the linearized equation for the superconducting order parameter in leading order of a 1/N expansion. The linearized equation is solved numerically on a square lattice taking instantaneous and retarded contributions into account. Classifying the order parameter according to irreducible representations of the point group C_4v of the square lattice and according to even or odd parity in frequency we find that a reasonably strong instability occurs only for even frequency pairing with d-wavelike symmetry. The corresponding transition temperature T_c is where t is the nearest-neighbor hopping integral. The underlying effective interaction consists of an attractive, instantaneous term and a retarded term due to charge and spin fluctuations. The latter is weakly attractive at low frequencies below ,strongly repulsive up to and attractive towards even higher energies. T_c increases with decreasing doping until a d-wavelike bond-order wave instability is encountered near optimal doping at for J=0.3. T_c is essentially linear in J and rather insensitive to an additional second-nearest neighbor hopping integral t'. A rather striking property of T_c is that it is hardly affected by the soft mode associated with the bond-order wave instability or by the Van Hove singularity in the case with second-nearest neighbor hopping. This unique feature reflects the fact that the solution of the gap equation involves momenta far away from the Fermi surface (due to the instantaneous term) and many frequencies (due to the retarded term) so that singular properties in momentum or frequency are averaged out very effectively. Received: 16 June 1998 / Accepted: 14 July 1998     

Electron correlation in two-dimensional systems: CHNC approach to finite-temperature and spin-polarization effects

Applying the classical-map hypernetted-chain method (CHNC) developed recently by Dharma-wardana and Perrot, we have studied the temperature and spin-polarization effects on electron correlation in the uniform quantum two-dimensional gas (2DEG) over a wide range of temperature T and spin-polarization ζ. The quantum fluid at the temperature T is mapped to a classical fluid at the temperature T_cf given by T_cf²=T²+T_q², where the quantum temperature T_q is determined by comparing the calculated correlation energy to that of Monte Carlo results for the fully spin-polarized quantum system at zero temperature. By the iterative solution of the modified HNC equation and the Ornstein-Zernike equation, we have obtained the pair distribution function (PDF) and correlation energy for the two-component classical 2DEG with a classical fluid temperature T_cf. The anti-parallel bridge function B₁₂(r) appearing in the modified HNC equation is determined by using the Monte Carlo correlation energy at T=0 or STLS (Singwi-Tosi-Land-Sjölander) result at T>0 and the numerical solution to the Percus-Yevick (PY) equation for the system of hard disks. By calculating the Pauli potential, the bridge function, PDFs, structure factors and correlation energy, we have shown that in some cases, the properties of the uniform quantum 2DEG depend remarkably on the temperature and spin-polarization.     

Phase behavior of a suspension of hard spherocylinders plus ideal polymer chains

We study isotropic-isotropic and isotropic-nematic phase transitions of fluid mixtures containing hard spherocylinders (HSC) and added non-adsorbing ideal polymer chains using scaled particle theory (SPT). First, we investigate isotropic-nematic (I -N phase coexistence using SPT in the absence of polymer. We compare the results obtained using a Gaussian form of the orientational distribution function (ODF) to minimize the free energy versus minimizing numerically. We find that formal numerical minimization gives results that are much closer to computer simulation results. In order to describe mixtures of HSC plus ideal chains we studied the depletion of ideal chains around a HSC. We analyze the density profiles of ideal chains near a hard cylinder and find the depletion thickness δ is a function of the ratio of the polymer's radius of gyration R_g and the cylinder radius R_c. Our results are compared with a common approximation in which the depletion thickness is taken equal to the radius of gyration of the polymer chain. We incorporate the correct depletion thickness into SPT and find that for R _g/R _c < 1.56 using ideal chains gives phase transitions at smaller polymer concentrations, whereas for R _g/R _c > 1.56 , which is a common experimental situation, the phase transitions are found at larger polymer concentrations with respect to δ = R _g . The differences are significant, especially for R _g ≫ R _c , so we can conclude it is essential to take into account the properties of ideal polymer chains and the resulting depletion near a cylinder. Finally, we present phase diagrams for rod-polymer mixtures which could be realized under experimental conditions.     

Some metallic properties in the framework of Tsallis generalized statistics

Some metallic quantities are calculated on the grounds of Tsallis generalized statistics: the specific heat at constant volume, c _V (T); the chemical potential, ; the Pauli paramagnetic susceptibility, and the Korringa constant, . First it is found that for a general value of q, the Sommerfeld expansion series will exhibit both, odd and even terms, contrary to what is obtained if we use the Fermi-Dirac (FD) statistics, where only even terms appear. It follows that: (i) the specific heat coefficient, , is q-dependent, but the temperature dependence of c_V remains linear, as in the FD case; (ii) the Fermi energy, , differs from the chemical potential by a linear term in T, and not quadratic, as in FD, the same happening for ; (iii) the Korringa constant is q-dependent, but not T-dependent. In the limit the results of FD statistics are recovered. Metallic thin films and multilayers exhibiting fractal surface structures are possible systems where the present results could be tested. Received 30 June 1999 and Received in final form 7 September 1999     

Giant magneto-optical response of ferromagnetic EuB<Subscript><Emphasis Type="Bold">6</Emphasis></Subscript>

Intercalation of polyatomic molecules into a superconductor can drastically affect the properties of the compound. A mechanism responsible for a large increase in T _c for such systems is proposed. It explains the recent remarkable observation of high T _c superconductivity in the hole-doped C₆₀/CHX₃ (X≡Cl, Br) compounds and the large shift in their T _c upon Cl↦Br substitution. The increase in T _c is due to contribution to the pairing arising from the interaction of electrons with the vibrational manifold of the molecule. The proposed mechanism opens up the possibility to observe a site-selective isotope effect. We also suggest that intercalating CHI₃ would further increase the critical temperature to T _c≃ 140 K. Received 23 January 2002     

A simple theory for high Δ T c ratio in d-wave superconductors

We investigate a simple explanation for the high maximum gap to T _c ratio found experimentally in high T _c compounds. We ascribe this observation to the lowering of T _c by boson scattering of electrons between parts of the Fermi surface with opposite sign for the order parameter. We study the simplest possible model within this picture. Our quantitative results show that we can account for experiment for a rather small value of the coupling constant, all the other ingredients of our model being already known to exist in these compounds. A striking implication of this theory is the fairly high value of the critical temperature in the absence of boson scattering. Received 12 March 2001 and Received in final form 25 May 2001     

Quantum chemical construction of a reduced reaction Hamiltonian and T 1 -relaxation and pure T 2 -dephasing rates for the proton transfer in 3-chlorotropolone

Separating multidimensional problems into that of a relevant system which is coupled to a bath of harmonic oscillators is a common concept in condensed phase theory. Focusing on the specific problem of intramolecular proton transfer in an isolated tropolone derivative, we consider the reactive proton moving in the plane of the molecule as the system and the remaining substrate normal modes as the bath. An all-Cartesian system-plus-substrate Hamiltonian is constructed employing density functional theory. It is then used to determine the temperature-dependent effective reduced reaction Hamiltonian and the state-to-state dissipation rates induced via the system-substrate coupling up to the bi-quadratic order. The important substrate modes for the T₁-relaxation and the pure T₂-dephasing rates, which are either intra- or inter-well in nature, are identified numerically and analyzed physically with molecular details. Received 19 November 2001 and Received in final form 19 February 2002     

The role of the amorphous phase in the re-crystallization process of cold-crystallized poly(ethylene terephthalate)

The process of re-crystallization in poly(ethylene terephthalate) is studied by means of X-ray diffraction (SAXS and WAXS) and dynamical mechanical thermal analysis. Samples cold-crystallized for 9h at the temperatures T _c = 100 fcir#circ;C and T _c = 160 fcir#circ;C, i.e. in the middle of the relaxation region and close to its upper bound, respectively, are analyzed. During heating from room temperature, a structural rearrangement of the stacks is always found at T _r ≃ T _c + 20 fcir#circ;C. This process is characterized by a decrease of the linear crystallinity, irrespective of T_c; on the other hand, the WAXS crystallinity never increases with T below T_c+30fcir#circ;C. The lamellar thickness in the low-T_c sample decreases significantly after the structural transition, whereas in the high-T_c sample the lamellar thickness remains almost unchanged. In both, high- and low-T_c, the interlamellar thickness increases above T_r. Moreover, the high-T_c sample shows a lower rate of decrease of the mechanical performance with increasing T as the threshold T_r is crossed. This result is interpreted in terms of the formation of rigid amorphous domains where the chains are partially oriented. The presence of these domains would determine i) the stabilization of the crystalline lamellae from the thermodynamic point of view and ii) the increase of the elastic modulus of the amorphous interlamellar regions. This idea is discussed by resorting to a phase diagram. An estimation of the chemical-potential increase of the interlamellar amorphous regions, due to the enhancement of the structural constraints hindering segmental mobility, is offered. Finally, previous calculations developed within the framework of the Gaussian chain model (F.J. Baltá Calleja et al., Phys. Rev. B 75, 224201 (2007)) are used here to estimate the degree of chain orientation induced by the structural transition of the stacks.     

Frequency-dependent fluctuational conductivity above in anisotropic superconductors: effects of a short wavelength cutoff

We discuss the excess conductivity at nonzero frequencies in a superconductor above T_c within the Gaussian approximation. We focus the attention on the temperature range not too close to T_c: within a time-dependent Ginzburg-Landau formulation, we phenomenologically introduce a short wavelength cutoff (of the order of the inverse coherence length) in the fluctuational spectrum to suppress high momentum modes. We treat the general cases of thin wires, anisotropic thin films and anisotropic bulk samples. We obtain in all cases explicit expressions for the finite frequency fluctuational conductivity. The dc case directly follows. Close to T_c the cutoff has no effect, and the known results for Gaussian fluctuations are recovered. Above T_c, and already for ε = ln(T/T _c) > 10^-2, we find strong suppression of the paraconductivity as compared to the Gaussian prediction, in particular in the real part of the paraconductivity. At high ε the cutoff effects are dominant. We discuss our results in comparison with data on high-T_c superconductors. Received 19 March 2002 Published online 25 June 2002     

电子型掺杂高温超导体La2-xCexCuO4飞秒时间分辨动力学研究

利用飞秒时间分辨光抽运探测技术研究了电子型掺杂La_2-xCe_xCuO₄(LCCO)高温超导材料的准粒子超快动力学过程.得到低温(T<0.7T_c)、转变温度附近(0.7T_c≤T≤T_c)和高温(T>T_c)三个温区内的动力学行为.研究发 关键词： 电子型掺杂高温超导体 飞秒时间分辨 准粒子 声子瓶颈