Effect of mixing and spatial dimension on the glass transition

We study the influence of composition changes on the glass transition of binary hard disc and hard sphere mixtures in the framework of mode coupling theory. We derive a general expression for the slope of a glass transition line. Applied to the binary mixture in the low concentration limits, this new method allows a fast prediction of some properties of the glass transition lines. The glass transition diagram we find for binary hard discs strongly resembles the random close packing diagram. Compared to 3D from previous studies, the extension of the glass regime due to mixing is much more pronounced in 2D where plasticization only sets in at larger size disparities. For small size disparitie…

Glass transition of hard spheres in high dimensions

We have investigated analytically and numerically the liquid-glass transition of hard spheres for dimensions $d\to \infty $ in the framework of mode-coupling theory. The numerical results for the critical collective and self nonergodicity parameters $f_{c}(k;d) $ and $f_{c}^{(s)}(k;d) $ exhibit non-Gaussian $k$ -dependence even up to $d=800$. $f_{c}^{(s)}(k;d) $ and $f_{c}(k;d) $ differ for $k\sim d^{1/2}$, but become identical on a scale $k\sim d$, which is proven analytically. The critical packing fraction $\phi_{c}(d) \sim d^{2}2^{-d}$ is above the corresponding Kauzmann packing fraction $\phi_{K}(d)$ derived by a small cage expansion. Its quadratic pre-exponential factor is different fr…

A mode coupling analysis of the central peak at order disorder phase transitions

The influence of local and translation invariant memory effects on the critical dynamics of a model undergoing a continous structural phase transition from a disordered (T>Tc) to an ordered distorted phase (T>Tc) is studied by mode coupling theory above the critical temperatureTc. It is shown that besides the existence of critical slowing-down modes there also exists a central peak as a consequence of correlations of the critical modes, increasing with the critical exponent γ when approachingTc. The dependence of the central peak on the wavevector\(\vec q\), temperatureT and on the spatial dimensiond is investigated. Ford=3 a scenario withlocal long time memory correlations is compared with…

Strongly confined fluids: Diverging time scales and slowing down of equilibration

The Newtonian dynamics of strongly confined fluids exhibits a rich behavior. Its confined and unconfined degrees of freedom decouple for confinement length $L \to 0$. In that case and for a slit geometry the intermediate scattering functions $S_{\mu\nu}(q,t)$ simplify, resulting for $(\mu,\nu) \neq (0,0)$ in a Knudsen-gas like behavior of the confined degrees of freedom, and otherwise in $S_{\parallel}(q,t)$, describing the structural relaxation of the unconfined ones. Taking the coupling into account we prove that the energy fluctuations relax exponentially. For smooth potentials the relaxation times diverge as $L^{-3}$ and $L^{-4}$, respectively, for the confined and unconfined degrees of…

Location- and observation time-dependent quantum-tunneling

We investigate quantum tunneling in a translation invariant chain of particles. The particles interact harmonically with their nearest neighbors, except for one bond, which is anharmonic. It is described by a symmetric double well potential. In the first step, we show how the anharmonic coordinate can be separated from the normal modes. This yields a Lagrangian which has been used to study quantum dissipation. Elimination of the normal modes leads to a nonlocal action of Caldeira-Leggett type. If the anharmonic bond defect is in the bulk, one arrives at Ohmic damping, i.e. there is a transition of a delocalized bond state to a localized one if the elastic constant exceeds a critical value $…

Test of molecular mode coupling theory for general rigid molecules

We report recent progress on the test of mode coupling theory for molecular liquids (MMCT) for molecules of arbitrary shape. The MMCT equations in the long time limit are solved for supercooled water including all molecular degrees of freedom. In contrast to our earlier treatment of water as a linear molecule, we find that the glass-transition temperature ${T}_{c}$ is overestimated by the theory as was found in the case of simple liquids. The nonergodicity parameters are calculated from the ``full'' set of MMCT equations truncated at ${l}_{\mathrm{co}}=2.$ These results are compared (i) with the nonergodicity parameters from MMCT with ${l}_{\mathrm{co}}=2$ in the ``dipole'' approximation ${…

Effective kink-kink interaction in a one-dimensional model mediated by phonon exchange

The general 1D double-well model with anharmonic interaction is considered in the displacive limit. Expansion of the Hamiltonian around a multikink state results in a phonon-kink Hamiltonian. It is shown that at rather low temperatures and short wave lengths the phonon-kink interaction can be treated in Born approximation, leading to a decomposition of the multikink-phonon Hamiltionian. Elimination of the phonons results in an effective potential for the kink-kink interaction, which corresponds to the one-dimensional analog of the RKKY interaction. This long-range interaction is inherent only for models with anharmonic on-site potentials and not in case of a double-parabola model.

Fluids in extreme confinement.

For extremely confined fluids with two-dimensional density $n$ in slit geometry of accessible width $L$, we prove that in the limit $L\to 0$ the lateral and transversal degrees of freedom decouple, and the latter become ideal-gas-like. For small wall separation the transverse degrees of freedom can be integrated out and renormalize the interaction potential. We identify $n L^2 $ as hidden smallness parameter of the confinement problem and evaluate the effective two-body potential analytically, which allows calculating the leading correction to the free energy exactly. Explicitly, we map a fluid of hard spheres in extreme confinement onto a 2d-fluid of disks with an effective hard-core diame…

Molecular correlation functions for uniaxial ellipsoids in the isotropic state

We perform event-driven molecular dynamics simulations of a system composed by uniaxial hard ellipsoids for different values of the aspect-ratio and packing fraction . We compare the molecular orientational-dependent structure factors previously calculated within the Percus-Yevick approximation with the numerical results. The agreement between theoretical and numerical results is rather satisfactory. We also show that, for specific orientational quantities, the molecular structure factors are sensitive to the particle shape and can be used to distinguish prolate from oblate ellipsoids. A first-order theoretical expansion around the spherical shape and a geometrical analysis of the configura…

Molecular dynamics studies of 3D quasicrystals

Abstract The thermodynamic behaviour of monatomic and diatomic models of three-dimensional icosahedral quasicrystals has been studied in NVT and NPT ensembles using molecular dynamics simulations with atoms interacting via Lennard-Jones potentials. We also report on a microcanonical MD simulation of decagonal Al 65 Cu 20 Co 15 quasicrystals where an experimentally determined binary model has been used. To obtain stability in this latter case it is necessary to endow the atoms with effective pair potentials. No transitions to crystalline or amorphous phases were found for diatomic models. Monatomic models, however, display a certain stability only in the low-temperature region. In the range …

Saddle index properties, singular topology, and its relation to thermodynamic singularities for aϕ4mean-field model

We investigate the potential energy surface of a ${\ensuremath{\phi}}^{4}$ model with infinite range interactions. All stationary points can be uniquely characterized by three real numbers ${\ensuremath{\alpha}}_{+},{\ensuremath{\alpha}}_{0},{\ensuremath{\alpha}}_{\ensuremath{-}}$ with ${\ensuremath{\alpha}}_{+}+{\ensuremath{\alpha}}_{0}+{\ensuremath{\alpha}}_{\ensuremath{-}}=1$, provided that the interaction strength $\ensuremath{\mu}$ is smaller than a critical value. The saddle index ${n}_{s}$ is equal to ${\ensuremath{\alpha}}_{0}$ and its distribution function has a maximum at ${n}_{s}^{\mathrm{max}}=1∕3$. The density $p(e)$ of stationary points with energy per particle $e$, as well as…

Modified Mode Coupling Theory of Glassy Dynamics Generated by Entanglement

Increasing the density in systems with strong excluded volume interactions leads simultaneously to an increase of static correlations and a slowing down of the relaxational dynamics. Mode coupling theory in its present form describes this mechanism, satisfactorily. In contrast, for systems where entanglement is dominant, e.g. infinitely thin hard rods on a lattice, glassy dynamics is not driven by increasing static correlations but by entanglement. We show how mode coupling approximation can be modified such that non-vanishing vertices occur which might account for such pure entanglement effects.

Mode coupling approach to the ideal glass transition of molecular liquids: Linear molecules

The mode coupling theory (MCT) for the ideal liquid glass transition, which was worked out for simple liquids mainly by Gotze, Sjogren, and their co-workers, is extended to a molecular liquid of linear and rigid molecules. By use of the projection formalism of Zwanzig and Mori an equation of motion is derived for the correlators S[sub lm,l[sup (prime)]m[sup (prime)]]([bold q],t) of the tensorial one-particle density rho [sub lm]([bold q],t), which contains the orientational degrees of freedom for l(greater-than)0. Application of the mode coupling approximation to the memory kernel results into a closed set of equations for S[sub lm,l[sup (prime)]m[sup (prime)]]([bold q],t), which requires t…

Duality of reduced density matrices and their eigenvalues

For states of quantum systems of N particles with harmonic interactions we prove that each reduced density matrix ρ obeys a duality condition. This condition implies duality relations for the eigenvalues λk of ρ and relates a harmonic model with length scales ${{\ell }_{1}},{{\ell }_{2}},\ldots ,{{\ell }_{N}}$ with another one with inverse lengths $1/{{\ell }_{1}},1/{{\ell }_{2}},\ldots ,1/{{\ell }_{N}}$. Entanglement entropies and correlation functions inherit duality from ρ. Self-duality can only occur for noninteracting particles in an isotropic harmonic trap.

Kinetic-Ising-model description of Newtonian dynamics: A one-dimensional example.

We show that the Newtonian dynamics of a chain of particles with an anharmonic on-site potential and harmonic nearest-neighbor interactions can be described by a one-dimensional kinetic Ising model with most general Glauber transition rates, provided the temperature is low enough compared to the minimum barrier height. The transition rates are calculated by use of the transition-state theory. At higher temperatures, memory effects occur which invalidate this kinetic description. These memory effects are due to the appearance of dynamically correlated clusters of particles performing periodic oscillations over a certain time scale.

Structural quantities of quasi-two-dimensional fluids

Quasi-two-dimensional fluids can be generated by confining a fluid between two parallel walls with narrow separation. Such fluids exhibit an inhomogeneous structure perpendicular to the walls due to the loss of translational symmetry. Taking the transversal degrees of freedom as a perturbation to an appropriate 2D reference fluid we provide a systematic expansion of the $m$-particle density for arbitrary $m$. To leading order in the slit width this density factorizes into the densities of the transversal and lateral degrees of freedom. Explicit expressions for the next-to-leading order terms are elaborated analytically quantifying the onset of inhomogeneity. The case $m=1$ yields the densit…

Regular packings on periodic lattices.

We investigate the problem of packing identical hard objects on regular lattices in d dimensions. Restricting configuration space to parallel alignment of the objects, we study the densest packing at a given aspect ratio X. For rectangles and ellipses on the square lattice as well as for biaxial ellipsoids on a simple cubic lattice, we calculate the maximum packing fraction \phi_d(X). It is proved to be continuous with an infinite number of singular points X^{\rm min}_\nu, X^{\rm max}_\nu, \nu=0, \pm 1, \pm 2,... In two dimensions, all maxima have the same height, whereas there is a unique global maximum for the case of ellipsoids. The form of \phi_d(X) is discussed in the context of geomet…

Molecular mode-coupling theory applied to a liquid of diatomic molecules

We study the molecular mode coupling theory for a liquid of diatomic molecules. The equations for the critical tensorial nonergodicity parameters ${\bf F}_{ll'}^m(q)$ and the critical amplitudes of the $\beta$ - relaxation ${\bf H}_{ll'}^m(q)$ are solved up to a cut off $l_{co}$ = 2 without any further approximations. Here $l,m$ are indices of spherical harmonics. Contrary to previous studies, where additional approximations were applied, we find in agreement with simulations, that all molecular degrees of freedom vitrify at a single temperature $T_c$. The theoretical results for the non ergodicity parameters and the critical amplitudes are compared with those from simulations. The qualitat…

Many-body Landau-Zener effect at fast sweep

The asymptotic staying probability P in the Landau-Zener effect with interaction is analytically investigated at fast sweep, epsilon = pi Delta^2/(2 hbar v) << 1. We have rigorously calculated the value of I_0 in the expansion P =~ 1 - epsilon + epsilon^2/2 + epsilon^2 I_0 for arbitrary couplings and relative resonance shifts of individual tunneling particles. The results essentially differ from those of the mean-field approximation. It is shown that strong long-range interactions such as dipole-dipole interaction (DDI) generate huge values of I_0 because flip of one particle strongly influences many others. However, in the presence of strong static disorder making resonance for indiv…

Glassy behavior of molecular crystals: A comparison between results from MD-simulation and mode coupling theory

We have investigated the glassy behavior of a molecular crystal built up with chloroadamantane molecules. For a simple model of this molecule and a rigid fcc lattice a MD simulation was performed from which we obtained the dynamical orientational correlators $S_{\lambda \lambda '}({\bf{q}},t)$ and the ``self'' correlators $S_{\lambda \lambda '}^{(s)}(t)$, with $\lambda = (\ell, m)$, $\lambda' = (\ell', m')$. Our investigations are for the diagonal correlators $\lambda = \lambda'$. Since the lattice constant decreases with decreasing temperature which leads to an increase of the steric hindrance of the molecules, we find a strong slowing down of the relaxation. It has a high sensitivity on $…

Event-Driven Simulation of the Dynamics of Hard Ellipsoids

We introduce a novel algorithm to perform event-driven simulations of hard rigid bodies of arbitrary shape, that relies on the evaluation of the geometric distance. In the case of a monodisperse system of uniaxial hard ellipsoids,we perform molecular dynamics simulations varying the aspect-ratio X0 and the packing fraction phi. We evaluate the translational Dtrans and the rotational Drot diffusion coefficient and the associated isodiffusivity lines in the phi-X0 plane. We observe a decoupling of the translational and rotational dynamics which generates an almost perpendicular crossing of the Dtrans and Drot isodiffusivity lines. While the self intermediate scattering function exhibits stret…

Mode-coupling theory of the glass transition for confined fluids

We present a detailed derivation of a microscopic theory for the glass transition of a liquid enclosed between two parallel walls relying on a mode-coupling approximation. This geometry lacks translational invariance perpendicular to the walls, which implies that the density profile and the density-density correlation function depends explicitly on the distances to the walls. We discuss the residual symmetry properties in slab geometry and introduce a symmetry adapted complete set of two-point correlation functions. Since the currents naturally split into components parallel and perpendicular to the walls the mathematical structure of the theory differs from the established mode-coupling eq…

Reference-point-independent dynamics of molecular liquids and glasses in the tensorial formalism.

We apply the tensorial formalism to the dynamics of molecular liquids and glasses. This formalism separates the degrees of freedom into translational and orientational ones. Using the Mori-Zwanzig projection formalism, the equations of motion for the tensorial density correlators S(lmn,l'm'n')(q-->,t) are derived. For this we show how to choose the slow variables such that the resulting Mori-Zwanzig equations are covariant under a change of the reference point of the body fixed frame. We also prove that the memory kernels obtained from mode-coupling theory (MCT) including all approximations preserve the covariance. This covariance makes, e.g., the glass transition point, the two universal s…

Molecular mode-coupling theory for supercooled liquids: application to water.

We present mode-coupling equations for the description of the slow dynamics observed in supercooled molecular liquids close to the glass transition. The mode-coupling theory (MCT) originally formulated to study the slow relaxation in simple atomic liquids, and then extended to the analysis of liquids composed by linear molecules, is here generalized to systems of arbitrarily shaped, rigid molecules. We compare the predictions of the theory for the $q$-vector dependence of the molecular nonergodicity parameters, calculated by solving numerically the molecular MCT equations in two different approximation schemes, with ``exact'' results calculated from a molecular dynamics simulation of superc…

Dynamical precursor of nematic order in a dense fluid of hard ellipsoids of revolution

We investigate hard ellipsoids of revolution in a parameter regime where no long range nematic order is present but already finite size domains are formed which show orientational order. Domain formation leads to a substantial slowing down of a collective rotational mode which separates well from the usual microscopic frequency regime. A dynamic coupling of this particular mode into all other modes provides a general mechanism which explains an excess peak in spectra of molecular fluids. Using molecular dynamics simulation on up to 4096 particles and on solving the molecular mode coupling equation we investigate dynamic properties of the peak and prove its orientational origin.

Inverse problem for the Landau-Zener effect

We consider the inverse Landau-Zener problem which consists in finding the energy-sweep functions W(t)=E1(t)-E2(t) resulting in the required time dependences of the level populations for a two-level system crossing the resonance one or more times during the sweep. We find sweep functions of particular forms that let manipulate the system in a required way, including complete switching from the state 1 to the state 2 and preparing the system at the exact ground and excited states at resonance.

Neutron scattering and molecular correlations in a supercooled liquid

We show that the intermediate scattering function $S_n(q,t)$ for neutron scattering (ns) can be expanded naturely with respect to a set of molecular correlation functions that give a complete description of the translational and orientational two-point correlations in the liquid. The general properties of this expansion are discussed with special focus on the $q$-dependence and hints for a (partial) determination of the molecular correlation functions from neutron scattering results are given. The resulting representation of the static structure factor $S_n(q)$ is studied in detail for a model system using data from a molecular dynamics simulation of a supercooled liquid of rigid diatomic m…

Test of the semischematic model for a liquid of linear molecules

We apply to a liquid of linear molecules the semischematic mode-coupling model, previously introduced to describe the center of mass (COM) slow dynamics of a network-forming molecular liquid. We compare the theoretical predictions and numerical results from a molecular dynamics simulation, both for the time and the wave-vector dependence of the COM density-density correlation function. We discuss the relationship between the presented analysis and the results from an approximate solution of the equations from molecular mode-coupling theory [R. Schilling and T. Scheidsteger, Phys. Rev. E 56 2932 (1997)].

Fluctuating hydrodynamics and diffusion in amorphous solids

The fluctuating hydrodynamic description for an isotropic fluid is extended to include the displacement field u, reflecting the freezing of the local structures in an amorphous solid. The fluctuating nonlinear equations for the set of hydrodynamic variables including u has been obtained. The role of u is manifested through its longitudinal part, i.e., \ensuremath{\nabla}\ensuremath{\cdot}u, in terms of which we define the variable c(x,t). It refers to the diffusion of the free volume or vacancies, signifying configurational rearrangements in the amorphous solid. The analysis here shows that one recovers the earlier result obtained by Das and Mazenko [Phys. Rev. A 34, 2265 (1986)] for mode c…

Nonlocality and fluctuations near the optical analog of a sonic horizon

We consider the behavior of fluctuations near the sonic horizon and the role of the nonlocality of interaction (nonlinearity) on their regularization. The nonlocality dominates if its characteristic length scale is larger than the regularization length. The influence of nonlocality may be important in the current experiments on the transonic flow in Kerr nonlinear media. Experimental conditions, under which the observation of straddled fluctuations can be observed, are discussed.

Ideal glass transitions for hard ellipsoids

For hard ellipsoids of revolution we calculate the phase diagram for the idealized glass transition. Our equations cover the glass physics in the full phase space, for all packing fractions and all aspect ratios X$_0$. With increasing aspect ratio we find the idealized glass transition to become primarily be driven by orientational degrees of freedom. For needle or plate like systems the transition is strongly influenced by a precursor of a nematic instability. We obtain three types of glass transition lines. The first one ($\phi_c^{(B)}$) corresponds to the conventional glass transition for spherical particles which is driven by the cage effect. At the second one ($\phi_c^{(B')}$) which oc…

Mode coupling theory for molecular liquids: What can we learn from a system of hard ellipsoids?

Molecular fluids show rich and complicated dynamics close to the glass transition. Some of these observations are related to the fact that translational and orientational degrees of freedom couple in nontrivial ways. A model system which can serve as a paradigm to understand these couplings is a system of hard ellipsoids of revolution. To test this we compare at the ideal glass transition the static molecular correlators of a linear A-B Lennard-Jones molecule obtained from a molecular dynamics simulation with a selected fluid of hard ellipsoids for which the static correlators have been obtained using Percus-Yevick theory. We also demonstrate that the critical non-ergodicity parameters obta…

Delocalization-Localization Transition due to Anharmonicity

Analytical and numerical calculations for a reduced Fermi-Pasta-Ulam chain demonstrate that energy localization does not require more than one conserved quantity. Clear evidence for the existence of a sharp delocalization-localization transition at a critical amplitude is given. Approaching the critical amplitude from above and below, diverging time scales occur. Above the critical amplitude, the energy packet converges towards a discrete breather. Nevertheless, ballistic energy transportation is present, demonstrating that its existence does not necessarily imply delocalization.

Intrinsic stability of quasicrystals under the generation of Frenkel pairs

Under irradiation metastable quasicrystals undergo a phase transition to an amorphous state. This transition can be reversed by annealing. As in normal crystalline materials the phase transition is considered to be triggered by generation and recombination of vacancies and interstitial atoms (Frenkel pairs). We have classified the possible Frenkel defects in a metastable monatomic quasicrystal with respect to geometric and energetic properties. With numerical simulation we have studied the behaviour of the quasicrystal under a load of Frenkel defects for various defect concentrations. We find three ranges of behaviour: up to 5% defects per atom the structure remains icosahedral, in a middle…

Nucleation of quasicrystals by rapid cooling of a binary melt: A molecular-dynamics study.

A binary Lennard-Jones fluid was cooled in an NPT ensemble by molecular-dynamics simulations. Depending on the cooling rate, we find a sharp transition from the melt either into a disordered structure or into a phase of icosahedral long-range order. We also observed a decagonal phase.

HIERARCHICAL MELTING OF ONE-DIMENSIONAL INCOMMENSURATE STRUCTURES

We study the low—temperature properties of quasi one—dimensional, incommensurate structures which are described by a Frenkel—Kontorova—like model. A new type of renormalization method will be presented, which is determined by the continued fraction expansion of the incommensurability ratio ζ. (This method yields a hierarchy of renormalized Hamiltonians ϰ(n,p) describing the thermal behavior for temperatures T = O(T(n,p)), where T(n,p) follows from the continued fraction expansion of ζ. By means of this method the low—temperature specific heat c(T) and the static structure factor S(q) are calculated for fixed ζ. c(T) possesses a hierarchy of Schottky anomalies related to the rational approxi…

Dynamics of the rotational degrees of freedom in a supercooled liquid of diatomic molecules

Using molecular dynamics computer simulations, we investigate the dynamics of the rotational degrees of freedom in a supercooled system composed of rigid, diatomic molecules. The interaction between the molecules is given by the sum of interaction-site potentials of the Lennard-Jones type. In agreement with mode-coupling theory (MCT), we find that the relaxation times of the orientational time correlation functions C_1^(s), C_2^(s) and C_1 show at low temperatures a power-law with the same critical temperature T_c, and which is also identical to the critical temperature for the translational degrees of freedom. In contrast to MCT we find, however, that for these correlators the time-tempera…

Universal mechanism of spin relaxation in solids

We consider relaxation of a rigid spin cluster in an elastic medium in the presence of the magnetic field. Universal simple expression for spin-phonon matrix elements due to local rotations of the lattice is derived. The equivalence of the lattice frame and the laboratory frame approaches is established. For spin Hamiltonians with strong uniaxial anisotropy the field dependence of the transition rates due to rotations is analytically calculated and its universality is demonstrated. The role of time reversal symmetry in spin-phonon transitions has been elucidated. The theory provides lower bound on the decoherence of any spin-based solid-state qubit.

Simulation of the dynamics of hard ellipsoids

We study a system of uniaxial hard ellipsoids by molecular dynamics simulations, changing both the aspect-ratio X-0 (X-0 = a/b, where a is the length of the revolution axis and b is the length of the two other axes) and the packing fraction phi. We calculate the translational and rotational mean squared displacements, the translational D-trans and the rotational D-rot diffusion coefficients and the associated isodiffusivity lines in the phi - X-0 plane. For the first time, we characterize the cage effect through the logarithmic time derivative of log and log . These quantities exhibit a minimum if the system is supercooled and we show that, consistently with our previous findings, for large…

Microscopic Dynamics of Hard Ellipsoids in their Liquid and Glassy Phase

To investigate the influence of orientational degrees of freedom onto the dynamics of molecular systems in its supercooled and glassy regime we have solved numerically the mode-coupling equations for hard ellipsoids of revolution. For a wide range of volume fractions $\phi$ and aspect ratios $x_{0}$ we find an orientational peak in the center of mass spectra $\chi_{000}^{''}(q,\omega)$ and $\phi_{000}^{''} (q,\omega)$ about one decade below a high frequency peak. This orientational peak is the counterpart of a peak appearing in the quadrupolar spectra $\chi_{22m}^{''}(q,\omega)$ and $\phi_{22m}^{''}(q,\omega)$. The latter peak is almost insensitive on $\phi$ for $x_{0}$ close to one, i.e. f…

Test of mode coupling theory for a supercooled liquid of diatomic molecules. II.q-dependent orientational correlators

Using molecular dynamics computer simulations we study the dynamics of a molecular liquid by means of a general class of time-dependent correlators S_{ll'}^m(q,t) which explicitly involve translational (TDOF) and orientational degrees of freedom (ODOF). The system is composed of rigid, linear molecules with Lennard- Jones interactions. The q-dependence of the static correlators S_{ll'}^m(q) strongly depend on l, l' and m. The time dependent correlators are calculated for l=l'. A thorough test of the predictions of mode coupling theory (MCT) is performed for S_{ll}^m(q,t) and its self part S_{ll}^{(s)m}(q,t), for l=1,..,6. We find a clear signature for the existence of a single temperature T…

Glass transitions and scaling laws within an alternative mode-coupling theory

Idealized glass transitions are discussed within an alternative mode-coupling theory (TMCT) proposed by Tokuyama [Physica A 395, 31 (2014)]. This is done in order to identify common ground with and differences from the conventional mode-coupling theory (MCT). It is proven that both theories imply the same scaling laws for the transition dynamics, which are characterized by two power-law decay functions and two diverging power-law time scales. However, the values for the corresponding anomalous exponents calculated within both theories differ from each other. It is proven that the TMCT, contrary to the MCT, does not describe transitions with continuously vanishing arrested parts of the corre…

Energy relaxation in a? 4 with long range interactions

We investigate the influence of long range interactions on the relaxation behaviour of a lattice model with an on-site potential ofϕ 4-type and “infinite” range harmonic interactions. For finite number of particlesN, it is shown that the autocorrelation functions of the fluctuations of the one-particle energiesE n(t) decays exponentially. The corresponding relaxation time τ is proportional toN and is given by τ(T, N) =Nτ0(T). The temperature dependent time scale τ0 can explicitly be related to the dynamics of a one-particle correlator of the noninteracting system. The results are derived using Mori-Zwanzig projection formalism. The corresponding memory kernel is calculated within a mode cou…

Number of metastable states of a chain with competing and anharmonicΦ4−like interactions

We investigate the number of metastable configurations of a Φ 4 -like model with competing and anharmonic interactions as a function of an effective coupling constant η. The model has piecewise harmonic nearest-neighbor and harmonic next-nearerst-neighbor interactions. The number M of metastable states in the configuration space increases exponentially with the number N of particles: M∞exp(vN). It is shown numerically that, outside the previously considered range |η|<1/3, v is approximately linearly decreasing with η for |η|<1 and that v=0 for η≥1. These findings can be understood by describing the metastable configurations as an arrangement of kink solitons whose width creases with η

Energy landscape properties studied using symbolic sequences

We investigate a classical lattice system with $N$ particles. The potential energy $V$ of the scalar displacements is chosen as a $\phi ^4$ on-site potential plus interactions. Its stationary points are solutions of a coupled set of nonlinear equations. Starting with Aubry's anti-continuum limit it is easy to establish a one-to-one correspondence between the stationary points of $V$ and symbolic sequences $\bm{\sigma} = (\sigma_1,...,\sigma_N)$ with $\sigma_n=+,0,-$. We prove that this correspondence remains valid for interactions with a coupling constant $\epsilon$ below a critical value $\epsilon_c$ and that it allows the use of a ''thermodynamic'' formalism to calculate statistical prope…

Multiparticle breathers for a chain with double-quadratic on-site potential

We investigate the existence and properties of multiparticle breathers for a one-dimensional model with harmonic nearest neighbor interactions where a group of r particles $(r=1,2,3,\dots{})$ perform interwell oscillations between both wells of a double-quadratic on-site potiential. We find two types of such breathers. For the first type the breather frequency $\ensuremath{\Omega}$ is within the single-particle oscillator spectrum, and the ``residence'' time of each breather particle in the left and right well is about the same. For the second breather $\ensuremath{\Omega}$ is below that spectrum, and the ratio ${\ensuremath{\tau}}_{L}/{\ensuremath{\tau}}_{R}$ of the residence time in the l…

Tunneling in a ?breathing? double well: Adiabatic and antiadiabatic limits and tunneling suppression

Tunneling in a piecewise harmonic potential coupled to a harmonic oscillator is considered by means of the path integral technique. The reduced propagator for the tunneling particle is calculated explicitly and the tunneling splitting is found in semiclassical approximation. The result holds for arbitrary values of the parameters of the system. From this the adiabatic and antiadiabatic approximations are obtained as particular cases and compared with the results obtained differently. The limit of a strong interaction is also considered. It is found that for strong interaction or equivalently for the harmonic frequency tending to zero the preexponential factor in the tunneling splitting tend…

Microscopic theory for the glass transition in a system without static correlations

We study the orientational dynamics of infinitely thin hard rods of length L, with the centers-of-mass fixed on a simple cubic lattice with lattice constant a.We approximate the influence of the surrounding rods onto dynamics of a pair of rods by introducing an effective rotational diffusion constant D(l),l=L/a. We get D(l) ~ [1-v(l)], where v(l) is given through an integral of a time-dependent torque-torque correlator of an isolated pair of rods. A glass transition occurs at l_c, if v(l_c)=1. We present a variational and a numerically exact evaluation of v(l).Close to l_c the diffusion constant decreases as D(l) ~ (l_c-l)^\gamma, with \gamma=1. Our approach predicts a glass transition in t…

Microscopic theory of glassy dynamics and glass transition for molecular crystals.

We derive a microscopic equation of motion for the dynamical orientational correlators of molecular crystals. Our approach is based upon mode coupling theory. Compared to liquids we find four main differences: (i) the memory kernel contains Umklapp processes, (ii) besides the static two-molecule orientational correlators one also needs the static one-molecule orientational density as an input, where the latter is nontrivial, (iii) the static orientational current density correlator does contribute an anisotropic, inertia-independent part to the memory kernel, (iv) if the molecules are assumed to be fixed on a rigid lattice, the tensorial orientational correlators and the memory kernel have …

Spatially chaotic configurations and functional equations with rescaling

The functional equation is associated with the appearance of spatially chaotic structures in amorphous (glassy) materials. Continuous compactly supported solutions of the above equation are of special interest. We shall show that there are no such solutions for , whereas such a solution exists for almost all . The words `for almost all q' in the previous sentence cannot be omitted. There are exceptional values of q in the interval for which there are no integrable solutions. For example, , which is the reciprocal of the `golden ratio' is such an exceptional value. More generally, if is any Pisot - Vijayaraghavan number, or any Salem number, then is an exceptional value.

Ornstein-Zernike equation and Percus-Yevick theory for molecular crystals

We derive the Ornstein-Zernike equation for molecular crystals of axially symmetric particles and apply the Percus-Yevick approximation to this system. The one-particle orientational distribution function has a nontrivial dependence on the orientation and is needed as an input. Despite some differences, the Ornstein-Zernike equation for molecular crystals has a similar structure as for liquids. We solve both equations for hard ellipsoids on a sc lattice. Compared to molecular liquids, the tensorial orientational correlators exhibit less structure. However, depending on the lengths a and b of the rotation axis and the perpendicular axes of the ellipsoids, different behavior is found. For obl…

Quantum Spin-Tunneling:A Path Integral Approach

We investigate the quantum tunneling of a large spin in a crystal field and an external magnetic field. The twofold degeneracy of the corresponding classical ground state is removed due to tunneling. The tunnel splitting ΔE o of the ground state is calculated by use of a path integral formalism. It is shown that coherent spin state path integrals do not yield a reasonable result. However a “bosonlzation” of the spin system yields excellent results in the semiclassical limit. This result follows from the coherent spin state approach from replacing the spin quantum number s by s + 1/2 which causes a renormalization of the preexponential factor of ΔE o .

Mode-coupling theory for multiple decay channels

We investigate the properties of a class of mode-coupling equations for the glass transition where the density mode decays into multiple relaxation channels. We prove the existence and uniqueness of the solutions for Newtonian as well as Brownian dynamics and demonstrate that they fulfill the requirements of correlation functions, in the latter case the solutions are purely relaxational. Furthermore, we construct an effective mode-coupling functional which allows to map the theory to the case of a single decay channel, such that the covariance principle found for the mode-coupling theory for simple liquids is properly generalized. This in turn allows establishing the maximum theorem stating…

Test of mode coupling theory for a supercooled liquid of diatomic molecules.I. Translational degrees of freedom

A molecular dynamics simulation is performed for a supercooled liquid of rigid diatomic molecules. The time-dependent self and collective density correlators of the molecular centers of mass are determined and compared with the predictions of the ideal mode coupling theory (MCT) for simple liquids. This is done in real as well as in momentum space. One of the main results is the existence of a unique transition temperature T_c, where the dynamics crosses over from an ergodic to a quasi-nonergodic behavior. The value for T_c agrees with that found earlier for the orientational dynamics within the error bars. In the beta- regime of MCT the factorization of space- and time dependence is satisf…

Theories of the Structural Glass Transition

Microscopic dynamics of molecular liquids and glasses: Role of orientations and translation-rotation coupling

We investigate the dynamics of a fluid of dipolar hard spheres in its liquid and glassy phase, with emphasis on the microscopic time or frequency regime. This system shows rather different glass transition scenarios related to its rich equilibrium behavior which ranges from a simple hard sphere fluid to a long range ferroelectric orientational order. In the liquid phase close to the ideal glass transition line and in the glassy regime a medium range orientational order occurs leading to a softening of an orientational mode. To investigate the role of this mode we use the molecular mode-coupling equations to calculate the spectra $\phi_{lm}^{\prime \prime}(q,\omega)$ and $\chi _{lm}''(q,\ome…

Glassy dynamics in confinement: planar and bulk limits of the mode-coupling theory.

We demonstrate how the matrix-valued mode-coupling theory of the glass transition and glassy dynamics in planar confinement converges to the corresponding theory for two-dimensional (2D) planar and the three-dimensional bulk liquid, provided the wall potential satisfies certain conditions. Since the mode-coupling theory relies on the static properties as input, the emergence of a homogeneous limit for the matrix-valued intermediate scattering functions is directly connected to the convergence of the corresponding static quantities to their conventional counterparts. We show that the 2D limit is more subtle than the bulk limit, in particular, the in-planar dynamics decouples from the motion …

Diverging exchange force and form of the exact density matrix functional

For translationally invariant one-band lattice models, we exploit the ab initio knowledge of the natural orbitals to simplify reduced density matrix functional theory (RDMFT). Striking underlying features are discovered: First, within each symmetry sector, the interaction functional $\mathcal{F}$ depends only on the natural occupation numbers $\bf{n}$. The respective sets $\mathcal{P}^1_N$ and $\mathcal{E}^1_N$ of pure and ensemble $N$-representable one-matrices coincide. Second, and most importantly, the exact functional is strongly shaped by the geometry of the polytope $\mathcal{E}^1_N \equiv \mathcal{P}^1_N $, described by linear constraints $D^{(j)}(\bf{n})\geq 0$. For smaller systems,…

Glass transition for dipolar hard spheres: A mode-coupling approach

Abstract We apply the self-consistent mode-coupling equations, which were recently derived for molecular liquids, to a system of dipolar hard spheres. Making use of the direct correlation function in a mean spherical approximation and with a restriction of the rotational quantum number 1 to zero and one, we find three different phases in the η—T phase space. η and T denote the packing fraction and the temperature respectively. There is one phase where both the transitional degrees of freedom (TDOFs) and the orientational degrees of freedom (ODOFs) are ergodic (liquid), another phase with frozen TDOFs and ergodic ODOFs, and a third phase where TDOFs and ODOFs are frozen (glass). The dynamica…

Effects of nonlinear sweep in the Landau-Zener-Stueckelberg effect

We study the Landau-Zener-Stueckelberg (LZS) effect for a two-level system with a time-dependent nonlinear bias field (the sweep function) W(t). Our main concern is to investigate the influence of the nonlinearity of W(t) on the probability P to remain in the initial state. The dimensionless quantity epsilon = pi Delta ^2/(2 hbar v) depends on the coupling Delta of both levels and on the sweep rate v. For fast sweep rates, i.e., epsilon &lt;&lt; l and monotonic, analytic sweep functions linearizable in the vicinity of the resonance we find the transition probability 1-P ~= epsilon (1+a), where a&gt;0 is the correction to the LSZ result due to the nonlinearity of the sweep. Further increase …

Glass transition of binary mixtures of dipolar particles in two dimensions

We study the glass transition of binary mixtures of dipolar particles in two dimensions within the framework of mode-coupling theory, focusing in particular on the influence of composition changes. In a first step, we demonstrate that the experimental system of K\"onig et al. [Eur. Phys. J. E 18, 287 (2005)] is well described by point dipoles through a comparison between the experimental partial structure factors and those from our Monte Carlo simulation. For such a mixture of point particles we show that there is always a plasticization effect, i.e. a stabilization of the liquid state due to mixing, in contrast to binary hard disks. We demonstrate that the predicted plasticization effect i…

Nonadiabatic Transitions for a Decaying Two-Level-System: Geometrical and Dynamical Contributions

We study the Landau-Zener Problem for a decaying two-level-system described by a non-hermitean Hamiltonian, depending analytically on time. Use of a super-adiabatic basis allows to calculate the non-adiabatic transition probability P in the slow-sweep limit, without specifying the Hamiltonian explicitly. It is found that P consists of a ``dynamical'' and a ``geometrical'' factors. The former is determined by the complex adiabatic eigenvalues E_(t), only, whereas the latter solely requires the knowledge of \alpha_(+-)(t), the ratio of the components of each of the adiabatic eigenstates. Both factors can be split into a universal one, depending only on the complex level crossing points, and a…

Molecular correlations in a supercooled liquid

We present static and dynamic properties of molecular correlation functions S_{lmn,l'm'n'}(q,t) in a simulated supercooled liquid of water molecules, as a preliminary effort in the direction of solving the molecular mode coupling theory (MMCT) equations for supercooled molecular liquids. The temperature and time dependence of various molecular correlation functions, calculated from 250 ns long molecular dynamics simulations, show the characteristic patterns predicted by MMCT and shed light on the driving mechanism responsible for the slowing down of the molecular dynamics. We also discuss the symmetry properties of the molecular correlation functions which can be predicted on the basis of t…

Number-parity effect for confined fermions in one dimension

For $N$ spin-polarized fermions with harmonic pair interactions in a $1$-dimensional trap an odd-even effect is found. The spectrum of the $1$-particle reduced density matrix of the system's ground state differs qualitatively for $N$ odd and $N$ even. This effect does only occur for strong attractive and repulsive interactions. Since it does not exists for bosons, it must originate from the repulsive nature implied by the fermionic exchange statistics. In contrast to the spectrum, the $1$-particle density and correlation function for strong attractive interactions do not show any sensitivity on the number parity. This also suggests that reduced-density-matrix-functional theory has a more su…

Glass transition in confined geometry.

Extending mode-coupling theory, we elaborate a microscopic theory for the glass transition of liquids confined between two parallel flat hard walls. The theory contains the standard MCT equations in bulk and in two dimensions as limiting cases and requires as input solely the equilibrium density profile and the structure factors of the fluid in confinement. We evaluate the phase diagram as a function of the distance of the plates for the case of a hard sphere fluid and obtain an oscillatory behavior of the glass transtion line as a result of the structural changes related to layering.

Dynamics of Uniaxial Hard Ellipsoids

We study the dynamics of monodisperse hard ellipsoids via a new event-driven molecular dynamics algorithm as a function of volume fraction $\phi$ and aspect ratio $X_0$. We evaluate the translational $D_{trans}$ and the rotational $D_{rot}$ diffusion coefficient and the associated isodiffusivity lines in the $\phi-X_0$ plane. We observe a decoupling of the translational and rotational dynamics which generates an almost perpendicular crossing of the $D_{trans}$ and $D_{rot}$ isodiffusivity lines. While the self intermediate scattering function exhibits stretched relaxation, i.e. glassy dynamics, only for large $\phi$ and $X_0 \approx 1$, the second order orientational correlator $C_2(t)$ sho…