Statistical description of the sol-gel transition in systems with thermoreversible chemical bonds

A general statistical model is proposed for describing network-forming systems. The model is based on the representation of the partition function for all possible configurations of a thermoreversible network in the form of a functional integral over a scalar field. According to this model, two types of first-order phase transitions can occur in the systems under consideration: macroscopic phase separation with the structural phase transition due to the change in the configuration of the spatial network and the sol-gel transition due to the formation of a thermoreversible percolation cluster consisting of bound structural units. A detailed analysis is performed of the thermodynamic and structural properties of a solution of monomers that have f functional groups and can form thermoreversible chemical bonds. The influence of specific features of the chemical and volume interactions on the phase diagram of the system is investigated. The mutual position of the sol-gel transition line and the phase diagram is determined for different model parameters. It is revealed that two substantially different regimes of the behavior of the sol-gel transition line in the “temperature-volume fraction of structural units” plane are observed with a change in the rigidity of chemical bonds.     

Hydrogenated carbon clusters produced by highly charged ion impact on solid

The emission of small (hydrogenated) carbon cluster ions C_nHm ⁺ (n =2-22) upon highly charged Xe^q+ (q =20-44) impact on C₈₄ surfaces is studied by means of time-of-flight secondary ion mass spectrometry. The respective stage of hydrogenation/protonation of a certain carbon cluster ion Cn ⁺ is a strong indication for its geometrical structure. From the cluster ion yield as a function of cluster size it can be concluded, that the hydrogenation takes place after the initial carbon cluster formation. The carbon clusters seem to be emitted as an entity in agreement with “equilibrium” and “shock wave” models. Received 4 February 2000     

Analysis of the cluster formation in two-component cylindrical bottle-brush polymers under poor solvent conditions. A simulation study

Two-component bottle-brush polymers, where flexible side chains containing N = 20, 35 and 50 effective monomers are grafted alternatingly to a rigid backbone, are studied by Molecular Dynamics simulations, varying the grafting density s \sigma and the solvent quality. Whereas for poor solvents and large enough s \sigma the molecular brush is a cylindrical object with monomers of different type occupying locally the two different halves of the cylinder, for intermediate values of s \sigma an axially inhomogeneous structure of “pearl-necklace” type is formed, where microphase separation between monomers of different type within a cluster takes place. These “pearls” have a strongly non-spherical ellipsoidal shape, due to the fact that several side chains cluster together in one “pearl”. We discuss the resulting structures in detail and we present a comparison with the single-component bottle-brush case.     

On the dimensionality of superconductivity in cuprate superconductors

The question of the dimensionality of superconductivity is considered within the framework of a model of superconductivity via asymmetric, delocalized “crystalline” π orbitals (analogous to the corresponding molecular orbitals) extending along chains of covalently bonded copper and oxygen ions. It is shown that superconductivity is preceded by a separation of the bonds in the CuO₂ layer into covalent and ionic bonds with ordering of the covalent bonds into chains. Such an ordering facilitates the formation of a crystalline π orbital lowering the crystal energy by the resonance energy of the π bond and is therefore favored. The superconducting current is created by non-dissipative motion of π-electron pairs along the asymmetric, “crystalline” π orbitals extending along chains of covalently bonded copper and oxygen ions, in the presence of an ionic bond between neighboring chains extending through the easily polarizable O²⁻ ions. This ionic bond correlates the motion of the electron pairs along all the π orbitals and stabilizes the superconducting state. Only in this sense is the apparent “onedimensionality” of superconductivity in cuprate superconductors to be understood. Zh. Tekh. Fiz. 68, 82–84 (November 1998)     

The Birth of the Infinite Cluster:¶Finite-Size Scaling in Percolation

We address the question of finite-size scaling in percolation by studying bond percolation in a finite box of side length n, both in two and in higher dimensions. In dimension d= 2, we obtain a complete characterization of finite-size scaling. In dimensions d>2, we establish the same results under a set of hypotheses related to so-called scaling and hyperscaling postulates which are widely believed to hold up to d= 6. As a function of the size of the box, we determine the scaling window in which the system behaves critically. We characterize criticality in terms of the scaling of the sizes of the largest clusters in the box: incipient infinite clusters which give rise to the infinite cluster. Within the scaling window, we show that the size of the largest cluster behaves like n ^d π _n , where π _n is the probability at criticality that the origin is connected to the boundary of a box of radius n. We also show that, inside the window, there are typically many clusters of scale n ^d π _n , and hence that “the” incipient infinite cluster is not unique. Below the window, we show that the size of the largest cluster scales like ξ ^d π_ξ log(n/ξ), where ξ is the correlation length, and again, there are many clusters of this scale. Above the window, we show that the size of the largest cluster scales like n ^d P _∞, where P _∞ is the infinite cluster density, and that there is only one cluster of this scale. Our results are finite-dimensional analogues of results on the dominant component of the Erdős–Rényi mean-field random graph model. Received: 6 December 2000 / Accepted: 25 May 2001     

Quantum Fields, Cosmological Constant and Symmetry Doubling

We explore how energy-parity, a protective symmetry for the cosmological constant [Kaplan and Sundrum, 2005], arises naturally in the classical phase space dynamics of matter.We derive and generalize the Liouville operator of electrodynamics, incorporating a “varying alpha” and diffusion.In this model, a one-parameter deformation connects classical ensemble and quantum field theory. PACS:03.65.Ta, 03.70+k, 05.20.-y     

Thermodynamics of rotating self-gravitating systems

We investigate the statistical equilibrium properties of a system of classical particles interacting via Newtonian gravity, enclosed in a three-dimensional spherical volume. Within a mean-field approximation, we derive an equation for the density profiles maximizing the microcanonical entropy and solve it numerically. At low angular momenta, i.e. for a slowly rotating system, the well-known gravitational collapse “transition” is recovered. At higher angular momenta, instead, rotational symmetry can spontaneously break down giving rise to more complex equilibrium configurations, such as double-clusters (“double stars”). We analyze the thermodynamics of the system and the stability of the different equilibrium configurations against rotational symmetry breaking, and provide the global phase diagram. Received 8 July 2002 Published online 15 October 2002 RID="a" ID="a"e-mail: demartino@hmi.de     

Distortion of the Poisson Bracket by the Noncommutative Planck Constants

In this paper we introduce a kind of “noncommutative neighbourhood” of a semiclassical parameter corresponding to the Planck constant. This construction is defined as a certain filtered and graded algebra with an infinite number of generators indexed by planar binary leaf-labelled trees. The associated graded algebra (the classical shadow) is interpreted as a “distortion” of the algebra of classical observables of a physical system. It is proven that there exists a q-analogue of the Weyl quantization, where q is a matrix of formal variables, which induces a nontrivial noncommutative analogue of a Poisson bracket on the classical shadow.     

Classical dynamical simulation of spontaneous alloying

“Spontaneous alloying” observed by Yasuda, Mori et al. for metallic small clusters is simulated using classical Hamiltonian dynamics. Very rapid alloying occurs homogeneously and cooperatively starting from the solid phase of the cluster if the heat of solution is negative and the size of cluster is less than a critical size. Analysis of 2D models reveals that the alloying rate obeys an Arrhenius-type law, which predicts the alloying time much less than second at room temperature. Evidences manifesting that the spontaneous alloying proceeds in the solid phase without melting are also presented. The simulation reproduces the essential features of the experiments. Received: 2 March 1998 / Revised: 21 May 1998 / Accepted: 28 May 1998     

Theory of one-dimensional and quasi-one-dimensional heat conduction

It is shown that the heat conduction process in a one-dimensional flow of a fluid moving with a velocity V in a constant temperature field follows a law that is considerably more complicated than an “ordinary” exponential law. It is demonstrated that in the quasi-one-dimensional case the heat conduction process in an abstract space of dimension 1+ɛ, where ɛ varies from zero to unity, is described by a modified Fourier equation. Its solution for an infinite space is found. Zh. Tekh. Fiz. 67, 8–12 (July 1997)     

Application of symmetry operations for construction of quasiperiodic structures in a plane

A method is proposed for constructing a quasiperiodic structure of symmetry elements — regular pentagons and five-pointed stars — in a plane. The growth of the structure is determined by the action of the symmetry operations, whose effect is not completely identical to that of similar operations in classical crystallography. The tiling (“flower of pentagons”), consisting of a central pentagon and five side pentagons joined along the edges, is studied. The growth of this tiling is accompanied by the appearance of a “flower of stars” and by the formation of isolated pores in the form of rhombi. The relation between the obtained structure and Penrose tiling is examined, and it is noted that some vertices of the Penrose tiling coincide with all vertices of the polygons of the packing obtained. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 635–640 (25 April 1997)     

Higher equations of motion in the N = 1 SUSY Liouville field theory

As in the ordinary bosonic Liouville field theory, in its N = 1 supersymmetric version, an infinite set of operator valued relations, the “higher equations of motions,” hold. The equations are in one to one correspondence with the singular representations of the super Virasoro algebra and enumerated by a pair of natural numbers (m, n). We explicitly demonstrate these equations in the classical case, where the equations of type (1, n) survive and can be interpreted directly as relations for classical fields. The general form of higher equations of motion is established in the quantum case, both for the Neveu-Schwarz and Ramond series. The text was submitted by the authors in English.     

Quasiclassical description of electronic supershells in simple metal clusters

A quasiclassical method for calculating shell effects, which has been used previously in atomic and plasma physics, is used to describe electronic supershells in metal clusters. An analytical expression is obtained, in the spherical jellium model, for the oscillating part of the binding energy of electrons of a cluster as a sum of contributions from supershells with quantum numbers 2n _r +l, 3n _r +l, 4n _r +l,... This expression is written in terms of the classical characteristics of the motion of an electron with the Fermi energy in a self-consistent potential. The conditions under which a new supershell appears and the relative contribution of this shell are investigated as a function of the cluster size and form of the potential. Specific calculations are performed for a “square well” of finite depth. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 5, 333–337 (10 September 1999)     

Correlated Knowledge: an Epistemic-Logic View on Quantum Entanglement

In this paper we give a logical analysis of both classical and quantum correlations. We propose a new logical system to reason about the information carried by a complex system composed of several parts. Our formalism is based on an extension of epistemic logic with operators for “group knowledge” (the logic GEL), further extended with atomic sentences describing the results of “joint observations” (the logic LCK). As models we introduce correlation models, as a generalization of the standard representation of epistemic models as vector models. We give sound and complete axiomatizations for our logics, and we use this setting to investigate the relationship between the information carried by each of the parts of a complex system and the information carried by the whole system. In particular we distinguish between the “distributed information”, obtainable by simply pooling together all the information that can be separately observed in any of the parts, and “correlated information”, obtainable only by doing joint observations of the parts (and pooling together the results). Our formalism throws a new light on the difference between classical and quantum information and gives rise to an informational-logical characterization of the notion of “quantum entanglement”.     

Pseudogap and symmetry of superconducting order parameter in cuprates

The phase diagram, nature of the normal state pseudogap, type of the Fermi surface, and behavior of the superconducting gap in various cuprates are discussed in terms of a correlated state with valence bonds. The variational correlated state, which is a band analogue of the Anderson (RVB) states, is constructed using local unitary transformations. Formation of valence bonds causes attraction between holes in the d-channel and corresponding superconductivity compatible with antiferromagnetic spin order. Our calculations indicate that there is a fairly wide range of doping with antiferromagnetic order in isolated CuO₂ planes. The shape of the Fermi surface and phase transition curve are sensitive to the value and sign of the hopping interaction t′ between diagonal neighboring sites. In underdoped samples, the dielectrization of various sections of the Fermi boundary, depending on the sign of t′, gives rise to a pseudogap detected in photoemission spectra for various quasimomentum directions. In particular, in bismuth-and yttrium-based ceramics (t′>0), the transition from the normal state of overdoped samples to the pseudogap state of underdoped samples corresponds to the onset of dielectrization on the Brillouin zone boundary near k=(0,π) and transition from “large” to “small” Fermi surfaces. The hypothesis about s-wave superconductivity of La-and Nd-based ceramics has been revised: a situation is predicted when, notwithstanding the d-wave symmetry of the superconducting order parameter, the excitation energy on the Fermi surface does not vanish at all points of the phase space owing to the dielectrization of the Fermi boundary at k _x=± k _y. The model with orthorhombic distortions and two peaks on the curve of T _c versus doping is discussed in connection with experimental data for the yttrium-based ceramic. Zh. éksp. Teor. Fiz. 115, 649–674 (February 1999)     

DNA molecule as an elastic Heisenberg chain

A DNA molecule is simulated by an anisotropic elastic fiber which defines the configuration of the molecule central line and is supplemented with a chain of quantum two-level systems imitating hydrogen bonds between two polynucleotide chains in the DNA double helix. The system Hamiltonian consists of Kirchhoff’s classical elastic energy and the energy of a quantum anisotropic chain of “spins” 1/2. The two-level systems and macroscopic vector variables which determine the conformation of the central line are coupled by a classical vector field q, which is introduced to take into account the existence of two polynucleotide strands. Averaging over fast (microscopic) variables yields an effective potential U(q). In the approximation of weak coupling between the systems, the spectrum of elementary excitations and effective potential U(q) have been calculated in explicit form. The relation between elementary excitations in the “magnetic” subsystem and so-called breathing modes [C. Mandel, N. R. Kallenbach, and S. W. Englander, J. Mol. Biol. 135, 391 (1980); G. Manning, Biopolymers 22, 689 (1983)] corresponding to low-frequency excitations in DNA molecules is discussed. Zh. éksp. Teor. Fiz. 111, 1833–1844 (May 1997)     

Phase-sensitive reentrance into the normal state of mesoscopic SNS structures

Normal (N) metallic (Ag) mesoscopic conductors with two superconducting (S) faces (Al), arranged mirror-symmetrically relative to the streamlines of the current, periodically switch into the normal state as the superconducting phase difference Δϕ between the NS boundaries approaches the values Δϕ =(2n+1)π, n=0,1,2,..., irrespective of temperature and applied voltage. For Δϕ =2nπ and low applied voltages the conductance passes through a maximum and approaches the normal value as temperature decreases (reentrance). As the voltage subsequently increases, the conductance increases and passes through a maximum. As the phase difference moves away from the values Δϕ=2nπ, the maxima shift in the direction of low temperatures and voltages. The latter result shows unequivocally that in our metal structures it is necessary to take into account the next-order corrections to the “weak” proximity effect approximation. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 7, 489–494 (10 April 1998)     

Progressive construction of an “Olympic” gel

We consider a melt of cyclic polymers (N monomers per chain) containing a small volume fraction ϕ of open cycles (P monomers per chain, with P< N) with reactive ends. The reaction leads to the formation of small P-rings. If these P-rings trap a sufficient number ofN-rings, a macroscopic cluster (“Olympic” gel) will appear. Using a very primitive theory (where the statistics of knots is replaced by a statistics of proximity), we expect gelation to occur when ϕ > max P^1/2/N,(1/N) exp(const/P). Our study is restricted to N-rings that are small enough for their conformations to be Gaussian.     

Vibronic charge-transfer excitons: Possible nature of the unusual properties of virtual perovskitelike ferroelectrics

A vibronic charge-transfer exciton, which is a pair of Jahn-Teller electron and hole polarons, is considered as a possible cause of the appearance of the Müller phase in the virtual ferroelectric SrTiO₃ and the “green” luminescence in the virtual ferroelectric KTaO₃. The two “green” luminescence bands can be associated with emission from two states of a typical intrinsic defect, viz., a vibronic charge-transfer exciton trapped by an oxygen vacancy and an isolated vibronic charge-transfer exciton. In both cases the “green” luminescence corresponds to the recombination of the electron and the hole in the vibronic charge-transfer exciton, which is accompanied by the emission of light. The properties of the Müller phase can be attributed to mixing of the normal state and states of the vibronic charge-transfer exciton phase when they interact with polarization in the soft SrTiO₃ matrix under the conditions of a pseudo-Jahn-Teller (pseudo-JT) effect on a soft TO mode of the displacement type. In this case the vibronic charge-transfer exciton phase forming the low-lying excited states has “order-disorder” degrees of freedom and exists at temperatures significantly below the point of the order-disorder ferroelectric transition in SrTiO₃ at T=T Q≈37 K. The corresponding lowering of the symmetry of the vibronic charge-transfer exciton phase to polar symmetry leads to the possibility of a long-period incommensurate phase in such excited states, which arises as a result of the appearance of a Lifshitz invariant. The valence-band state making the largest contribution of the pseudo-JT effect corresponds to a wave vector equal to the critical wave vector of the incommensurate vibronic charge-transfer exciton phase. When the temperature is lowered, the pseudo-JT distortion increases down to ∼T _Q and subsequently saturates in accordance with the saturation of the dielectric constant. The basic assumption in the model is that the temperature T=T _Q corresponds to the narrow temperature range for the transition from an intermediate to a strong pseudo-JT effect under the conditions for the realization of polarization tunneling states. The appearance of a significant admixture of states of the modulated ferroelectric vibronic charge-transfer exciton phase to the ground state under the conditions for the realization of polarization tunneling states at low temperatures provides an explanation for the principal properties of the Müller phase. Fiz. Tverd. Tela (St. Petersburg) 40, 907–909 (May 1998)     

Two-dimensional mesoscopic dusty plasma clusters: Structure and phase transitions

A two-dimensional mesoscopic cluster of “dusty plasma” particles, which can be interpreted as a system of microparticles in an rf gas discharge, is investigated. The ground-state configurations and corresponding eigenfrequencies and eigenvectors are found for clusters of N=22–40 particles in a harmonic confining potential. It is shown that a change in the Debye screening length R of the particle charge in the plasma can cause structural transformations of the ground state of the system, manifested as first-order or second-order phase transitions with respect to the parameter R. The disorder (“melting”) of the clusters is analyzed in detail by Monte Carlo simulation and molecular dynamics. By varying the characteristic range of particle interaction in a cluster, it is possible to modulate its thermodynamic properties and the character of the phase transitions, thereby causing a controlled transition of the system into the fully ordered, orientationally disordered, or fully disordered state. The possibility of dusty plasma clusters coexisting in different states is discussed. Zh. éksp. Teor. Fiz. 116, 1300–1312 (October 1999)