Lattice Thermal Transport in the Homogeneous Cage-Like Compounds Cu3VSe4 and Cu3NbSe4: Interplay between Phonon-Phase Space,Anharmonicity, and Atomic Mass

Understanding the correlation between crystal structure and thermal conductivity in semiconductors is very important for designing heat-transport-related devices, such as high-performance thermoelectric materials and heat dissipation in micro-nano-scale devices. In this work, the lattice thermal conductivity ( ) of the cage-like compounds Cu₃VSe₄ and Cu₃NbSe₄ was investigated by experimental measurements and first-principles calculations. The experimental of Cu₃NbSe₄ is approximately 25 % lower than that of Cu₃VSe₄ at 300 K. The relevant important physical parameters, including the sound velocity, heat capacity, weighted phonon phase space (W), and third-order force constants along with atomic mass were theoretically analyzed. It is found that W is the dominant parameter in determining the , and the other factors only play a minor role. The physical origin is the relatively “soft” lattice of Cu₃NbSe₄ with heavier atomic mass. This research provides deep insight into the correlation between the thermal conductivity and crystal structure and paves the way for discovering high-performance thermal management device and thermoelectric materials with intrinsically low .     

CH bond activation in the presence or absence of oxygen or nitrous oxide

The reaction of C₂H₆with lattice oxygen, O^2- (in the absence of gaseous oxygen), or “adsorbedℍ oxygen (in the presence of gaseous oxygen) over NiMoO₄ catalysts has been performed and compared to C₃H₈ activation. The results obtained indicate that adsorbed oxygen exhibits a higher reactivity to C₂H₆, while lattice oxygen is more reactive relative to C₃H₈. Kinetic studies of these two reactions in presence of molecular oxygen have indeed shown that the ethane oxidative dehydrogenation (ODH) is dependent on the oxygen partial pressure, whilst on the contrary propane ODH is not. In order to confirm the presence of “adsorbed” oxygen for ethane activation, ODH tests have been performed with N₂O. On increasing temperature, the O^- adsorbed species enhances the mild oxidation of ethane. The activation energy of ethane consumption E_C2H6, relative to propane (E_C3H8 = 133 kJ/mol) is 145 kJ/mol. A possible mechanism is proposed for the oxidative dehydrogenation of ethane. This revised version was published online in August 2006 with corrections to the Cover Date.     

Significance of a volcano relation of fajans for hydration energies

A volcano-shaped relation between heats of solution of a series of salts and the difference of hydration energy of the ions of the salt was noted by Fajans. This relation has a maximum when the difference of hydration energy of the cation and anion approaches zero. A rationalization of this type of relation is proposed on the basis of sums of reciprocal radii terms which represent the dependence of electrostatic hydration energy on ion size. The general trend of heats of solution with ionic size in series of salts with either a common cation or a common anion is discussed.     

Synthesis, structure and physical properties of Ru ferrites: BaMRu5O11 (M=Li and Cu) and BaM′2Ru4O11 (M′=Mn, Fe and Co)

The synthesis, structure, and physical properties of five R-type Ru ferrites with chemical formula BaMRu₅O₁₁ (M=Li and Cu) and BaM′₂Ru₄O₁₁ (M′=Mn, Fe and Co) are reported. All the ferrites crystallize in space group P6₃/mmc and consist of layers of edge sharing octahedra interconnected by pairs of face sharing octahedra and isolated trigonal bipyramids. For M=Li and Cu, the ferrites are paramagnetic metals with the M atoms found on the trigonal bipyramid sites exclusively. For M′=Mn, Fe and Co, the ferrites are soft ferromagnetic metals. For M′=Mn, the Mn atoms are mixed randomly with Ru atoms on different sites. The magnetic structure for BaMn₂Ru₄O₁₁ is reported.     

Calculations of concentration dependences of chemical shifts for acrylamide in water—DMSO mixed solvent

The lattice model of associated solutions was used to calculate the concentration dependences of the chemical shifts of¹³C magnetic nuclei in the acrylamide molecule in water—DMSO solvent. Each pair of bonds between the acrylamide group containing a magnetic nucleus and the neighboring solvent molecule was assumed to additively contribute to the change in the chemical shift of the nucleus in question. The new approach affords the same accuracy in describing the experimental data at any ratios of the solution components. It was shown that the chemical shifts and the excess heat of mixing of the water—DMSO binary solution can be simultaneously described using the same set of energy parameters of the model. The model makes it possible to employ experimental data on chemical shifts for studying intermolecular interactions in solutions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1983–1987, October, 1998.     

Traveling waves for a four-compartment lattice epidemic system with exposed class and standard incidence

This paper is considering the problem of traveling wave solutions (TWS) for a susceptible-exposed-infectious-recovered (SEIR) epidemic model with discrete diffusion. The threshold condition for the existence and nonexistence of TWS is obtained. More specifically, such kind of solutions are governed by the threshold number ?₀. We can find a critical wave speed c^? if ?₀ > 1, by employing the Schauder's fixed point theorem, limiting argument and two-sided Laplace transform, we confirm that there exists TWS for c > c^?, while there exists no TWS for c < c^?. We also obtain the nonexistence of TWS for ?₀ ≤ 1. At last, we give some biological explanations from the epidemiological perspective.     

Metastable decay rates,asymptotic expansions,and analytic continuation of thermodynamic functions

The grand potentialP(z)/kT of the cluster model at fugacityz, neglecting interactions between clusters, is defined by a power series _n Q _n z ⁿ , whereQ _n , which depends on the temperatureT, is the partition function of a cluster of sizen. At low temperatures this series has a finite radius of convergencez _s . Some theorems are proved showing that ifQ _n , considered as a function ofn, is the Laplace transform of a function with suitable properties, thenP(z) can be analytically continued into the complexz plane cut along the real axis fromz _s to + and that (a) the imaginary part ofP(z) on the cut is (apart from a relatively unimportant prefactor) equal to the rate of nucleation of the corresponding metastable state, as given by Becker-Döring theory, and (b) the real part ofP(z) on the cut is approximately equal to the metastable grand potential as calculated by truncating the divergent power series at its smallest term.     

Algebraic spatial correlations in lattice gas automata violating detailed balance

In this paper we discuss the existence of generic long-range correlations in spatially homogeneous and stable equilibrium states of closed lattice gas automata whose stochastic collision rules violate the symmetry conditions of detailed balance and in addition satisfy local conservation laws. Such correlations occur even though the collision rules are strictly local and invariant under all symmetries of the lattice. First a phenomenological (Langevin equation) approach is discussed. Next we present a theoretical analysis on the basis of an approximate microscopic (ring kinetic) theory. This theory is used to calculate the amplitude ofr ^– tails in the spatial correlations, and the result is compared with computer simulations.     

New results for diffusion in Lorentz lattice gas cellular automata

New calculations to over ten million time steps have revealed a more complex diffusive behavior than previously reported of a point particle on a square and triangular lattice randomly occupied by mirror or rotator scatterers. For the square lattice fully occupied by mirrors where extended closed particle orbits occur, anomalous diffusion was still found. However, for a not fully occupied lattice the superdiffusion, first noticed by Owczarek and Prellberg for a particular concentration, obtains for all concentrations. For the square lattice occupied by rotators and the triangular lattice occupied by mirrors or rotators, an absence of diffusion (trapping) was found for all concentrations, except on critical lines, where anomalous diffusion (extended closed orbits) occurs and hyperscaling holds for all closed orbits withuniversal exponentsd _f =7/4 and =15/7. Only one point on these critical lines can be related to a corresponding percolation problem. The questions arise therefore whether the other critical points can be mapped onto a new percolation-like problem and of the dynamical significance of hyperscaling.     

Energy-level statistics of model quantum systems: Universality and scaling in a lattice-point problem

We investigate the statistics of the numberN(R, S) of lattice pointsnZ ², in an annular domain (R, w)=(R+w)A\RA, whereR, w>0. HereA is a fixed convex set with smooth boundary andw is chosen so that the area of (R, w) isS. The statistics comes fromR being taken as random (with a smooth density) in some interval [c ₁ T,c ₂,T],c ₂>c ₁>0. We find that in the limitT the variance and distribution of N=N(R; S)–S depend strongly on howS grows withT. There is a saturation regimeS/T, asT, in which the fluctuations in N coming from the two boundaries of are independent. Then there is a scaling regime,S/Tz, 0<z<, in which the distribution depends onz in an almost periodic way going to a Gaussian asz0. The variance in this limit approachesz for genericA, but can be larger for degenerate cases. The former behavior is what one would expect from the Poisson limit of a distribution for annuli of finite area.