Kinetic theory of dense fluids. III. Density dependence of transport coefficients for dense gases

The viscosity coefficient obtained in a previous paper of this series is calculated as a function of density by developing the N-particle collision operator into a dynamic cluster expansion. The excess transport coefficient Δη is given in an exponential form,

$\text{Δν=ν}{}_0\text{exp}\text{∑}\text{l=1}\text{∞}\text{β}{}_{\mathrm{l}}\text{n}{}^{\mathrm{l}}\text{?1}$

where η₀ is the two-body Chapman-Enskog result for the transport coefficient, n is the density, and β_l is a density-independent quantity consisting of connected cluster contributions of (l + 2) particles. Therefore, the leading term β₁ consists of connected three-body cluster contributions. The excess shear viscosity coefficient is calculated for a monatomic hard-sphere fluid by computing β_l up to the three-body contributions and the result is compared with the molecular dynamics result by Ashurst and Hoover and also with the experimental data on Ar at 75°C. In spite of the crudity of the potential model used and the approximations made the agreement is good. The result can be improved if l-body clusters (l ? 4) are included in the calculation. The thermal conductivity coefficient can be obtained in a similar form by using exactly the same procedure used for the viscosity coefficient.     

Density, viscosity, and excess properties of the binary mixture of diethylene glycol monomethyl ether + water at T = (293.15, 303.15, 313.15, 323.15, 333.15) K under atmospheric pressure

Densities and viscosities have been measured as a function of composition for the binary liquid mixture of diethylene glycol monomethyl ether CH₃O(CH₂)₂O(CH₂)₂OH + water at T = (293.15, 303.15, 313.15, 323.15, 333.15) K under atmospheric pressure. Densities were determined using a capillary pycnometer. Viscosities were measured with Ubbelohde capillary viscometer. From the experimental data, the excess molar volumes V^E, and viscosity deviations δη, and the excess energies of activation for viscous flow ΔG^*E were calculated. These data have been correlated by the Redlich–Kister type equations to obtain their coefficients and standard deviations. The results suggest that molecular interaction between diethylene glycol monomethyl ether and water is strong.     

Eley–Rideal reaction dynamics between O atoms on β-cristobalite (1 0 0) surface: A new interpolated potential energy surface and classical trajectory study

We present a theoretical study of the collisions of atomic oxygen with O-precovered β-cristobalite (1 0 0) surface. We have constructed a multidimensional potential energy surface for the O₂/β-cristobalite (1 0 0) system based mainly on a dense grid of density functional theory points by using the interpolation corrugation-reducing procedure. Classical trajectories have been computed for quasithermal (100–1500 K) and state-specific (e.g., collision energies between 0.01 and 4 eV) conditions of reactants for different O incident angles (θ_v). Atomic sticking and O_2(adsorbed) formation are the main processes, although atomic reflection and Eley–Rideal (ER) reaction (i.e., O₂ gas) are also significant, depending their reaction probabilities on the O incident angle. ER reaction is enhanced by temperature increase, with an activation energy derived from the atomic recombination coefficient (γ_O(θ_v = 0°, T)) equal to 0.24 ± 0.02 eV within the 500–1500 K range, in close agreement with experimental data. Calculated γ_O(θ_v = 0°, T) values compare quite well with available experimental γ_O(T) although a more accurate calculation is proposed. Chemical energy accommodation coefficient β_O(T) is also discussed as a function of ER and other competitive contributions.     

Thermogalvanic power and fast ion conduction in δ-Bi2O3 and δ-(Bi2O3)1−x(R2O3)x with R = Y, Tb---Lu

The thermogalvanic power (Seebeck coefficient) of O^2- conducting δ-Bi₂O₃ and δ-(Bi₂O₃)_1−x(Y₂O₃)_x has been measured directly as a function of temperature and partial oxygen pressure in N₂---O₂ mixtures. The of δ-(Bi₂O₃)_0.75(R₂O₃)_0.25 with R = Tb---Lu was indirectly determined using an isothermal concentration cell technique. Except for pure δ-Bi₂O₃, the heat of transport is much smaller than the activation energy for O^2- conduction for all materials. The vibrational freedom of O²⁻ ions in all δ-stabilized materials is reflected in their IR spectra at room temperature. Two prototypes of a thermogalvanic P_O2 meter were tested.     

Higher Fock Sectors in the Wick-Cutkosky Model

In the Wick-Cutkosky model we analyze nonperturbatively, in light-front dynamics, the contributions of two-body and higher Fock sectors to the total norm and electromagnetic form factor. It turns out that two- and three-body sectors always dominate. For a maximal value of the coupling constant α = 2π, corresponding to the zero bound-state mass M = 0, they contribute 90% to the norm. With decrease of α the two-body contribution increases up to 100%. The form factor asymptotic is always determined by a two-body sector.     

The role of heat-conducting walls in the measurement of heat and mass transport in transient grating experiments

We present a two-dimensional model to account for the role of heat-conducting walls in the measurement of heat transport and Soret-effect-driven mass transport in transient holographic grating experiments. Heat diffusion into the walls leads to non-exponential decay of the temperature grating. Under certain experimental conditions it can be approximated by an exponential function and assigned an apparent thermal diffusivity D_{th, app} < D_{th, s}, where D_th,s is the true thermal diffusivity of the sample. The ratio D_{th, app}/D_{th, s} depends on only three dimensionless parameters, d /l_s, κ_s/κ_w, and D_{th, s}/D_{th, w}. d is the grating period, l_s the sample thickness, κ_s and κ_w the thermal conductivities of sample and wall, respectively, and D_th,w the thermal diffusivity of the wall. If at least two measurements are performed at different d /l_s, both D_th,s and κ_s can be determined. Instead of costly solving PDEs, D_th,s can be obtained by finding the zero of an analytic function. For thin samples and large grating periods, heat conduction into the walls plays a predominant role and the concentration grating in binary mixtures is no longer one-dimensional. Nevertheless, the normalized heterodyne diffraction efficiency of the concentration grating remains unaffected and the true thermal and collective diffusion coefficient and the correct Soret coefficient are still obtained from a simple one-dimensional model.     

Two models for the transport properties of YBa2Cu3O7−δ in its normal state

The high-temperature superconductor YBa₂Cu₃O_7−δ in its normal state, shows unusual dependence of its transport properties on the oxygen deficiency parameter δ and on temperature: for δ ≈ 0 both the resistivity and the Hall number rise linearly with temperature, while the thermoelectric power is very small. In order to interpret this unusual combination of properties we propose two alternative models, a two-dimensional tight-binding wide-band model, and a narrow-band model. In the first case we assume scattering by a fully excited boson field, with a mean free path Λ ∝ 1/T. In the second model we assume a band composed of two parts, where the upper smaller part does not contribute to transport (as would result from the existence of a mobility edge), and Λ is independent of temperature. The calculated results are compared with experiments.     

High-Resolution Infrared Spectra of the ν2, ν3, ν4, and 2ν3 Bands of SO3

New measurements are reported for the infrared spectrum of sulfur trioxide, ³²S¹⁶O₃, with resolutions ranging from 0.0015 cm⁻¹ to 0.0025 cm⁻¹. Rovibrational constants have been measured for the fundamentals ν₂, ν₃, and ν₄ and the overtone band 2ν₃. Comparisons are made with the earlier high-resolution measurements on SO₃, and the high correlation among some of the constants related to the Coriolis coupling of the ν₂ and ν₄ levels is discussed in order to understand the areas of disagreement with the earlier work. Splittings of some of the levels are observed and the splitting constant for K=3 of the ground state is determined for the first time. Other observed splittings include the K=1 levels of 2ν₃ (l=2), the K=2 levels of ν₃ and ν₄, and the K=3 levels of ν₂. The analysis shows that there are level crossings between the l=0 and l=2 states of 2ν₃ that allow one to determine the separation of the subband centers for these two states even though access to the l=0 state from the ground state is electric-dipole forbidden. This is a generalized phenomenon that should be found for many other molecules with the same symmetry. The l-type resonance constant, q₃, that causes the splitting of the l₃=±1, k=±1 levels of ν₃ also couples the l₃=0 and 2 states of 2ν₃.     

Excess molar volumes, viscosities, and refractive indices for binary and ternary mixtures of {cyclohexanone (1) + N,N-dimethylacetamide (2) + N,N-diethylethanolamine (3)} at (298.15, 308.15, and 318.15) K

Densities ρ, viscosities η, and refractive indices n_D, of the binary and ternary mixtures formed by cyclohexanone + N,N-dimethylacetamide + N,N-diethylethanolamine were measured at (298.15, 308.15, and 318.15) K for the liquid region and at ambient pressure for the whole composition ranges. The excess molar volumes V_m^E, viscosity deviations Δη, and refractive index deviations Δn_D, were calculated from experimental densities and refractive indices. The excess molar volumes are positive over the mole fraction range for binary mixtures of cyclohexanone(1) + N,N-dimethylacetamide (2) and N,N-dimethylactamide (2) + N,N-diethylethanolamine (3) and increase with increasing temperatures from (298.15 to 318.15) K. The excess molar volumes of cyclohexanone (1) + N,N-diethylethanolamine (3) are S-shaped dependence on composition with negative values in the N,N-diethylethanolamine rich-region and positive values at the opposite extreme and increase with increasing temperatures from (298.15 to 318.15) K. The excess molar volumes are positive over the whole mole fraction ranges for the ternary mixtures at all temperatures. Viscosity deviations are negative over the mole fraction range for all binary and ternary mixtures and decrease with increasing temperatures from (298.15 to 318.15) K. Refractive index deviations are negative over the mole fraction range for all binary and ternary mixtures and increase with increasing temperatures from (298.15 to 318.15) K. The experimental data of constitute were correlated as a function of the mole fraction by using the Redlich–Kister equation for binary and , Cibulka, Jasinski and Malanowski , Singe et al., Pintos et al., Calvo et al., Kohler, and Jacob–Fitzner for ternary mixture, respectively. McAllister^'s three body, Hind, and Nissan–Grunberg models were used for correlating the kinematic and dynamic viscosity of binary mixtures. The experimental data of the constitute binaries are analyzed to discuss the nature and strength of intermolecular interactions in these mixtures.     

The effect of the relative position of the bandgap with respect to laser wavelength on the behaviour of DFWM in semiconductor-doped glasses

Degenerated four-wave mixing (DFWM) was realised in five commercial semiconductor-doped glasses (Corning CS3–66, CS3–67, CS3–68, CS3–69, CS3–70). The reflectivity obtained for each glass seems very dependent on the energy excess (E=hv–E _g) and relatively independant on l, the product of the absorption coefficient () by the sample thickness (l). The decay time of the DFWM signal was measured for each glass. The relaxation was found to be different when the photon energy is under or over the gap.     

Densities, excess molar volumes, and viscosities of the binary and ternary mixtures of {diethylcarbonate (1) + p-chloroacetophenone (2) + 1-hexanol (3)} at 303.15 K for the liquid region and at ambient pressure

Densities ρ, dynamic viscosities η, of the ternary mixture (diethylcarbonate + p-chloroacetophenone + 1-hexanol) and the involved binary mixtures (diethylcarbonate + p-chloroacetophenone), (diethylcarbonate + 1-hexanol), and (p-chloroacetophenone + 1-hexanol) have been measured over the whole composition range at 303.15 K for the liquid region and at ambient pressure. The data obtained are used to calculate excess molar volumes V_m^E, excess partial molar volumes V¯_m,i^E, limiting excess partial molar volumes V¯_m,i^E,∞, and viscosity deviations Δη, of the binary and ternary mixtures. The data of excess molar volumes of the binary systems were fitted to the Redlich–Kister equation while for the ternary system the Cibulka equation was used. The McAllister's four body, and Kalidas and Laddha interaction models are used to correlate the kinematic viscosities of binary and ternary mixtures, respectively, to determine the fitting parameters and the standard deviations. The experimental data of the constitute binaries and ternary are analyzed to discuss the nature and strength of intermolecular interactions in these mixtures.     

Families of commuting transfer matrices and integrable models with disorder

A family of commuting transfer matrices is shown to be associated to each symmetry transformation of a given Yang-Baxter algebra. This applies in lattices models and field theory.The Yang-Baxter algebra remains unchanged when an arbitrary parameter μ_l is associated to each lattice site. We generate in this way integrable one-dimensional hamiltonians with long-range couplings and disorder given by the <{;μ₁<};. These operators are lattice versions of the non-local charges in sigma models. As a simple example we get a Dzialozhinski-Moriya interaction with an arbitrary coupling per site from the six-vertex model. A similar model with a disordered magnetic field follows too. Their exact solution by an algebraic Bethe ansatz is presented. We derive the excitations spectrum in terms of the density of parameters (μ).As another application, the total spin S² is computed for a XXZ Heisenberg chain (μ_l ≡ 0) as a function of the anisotropy Δ (− ∞ < Δ < + ∞).     

Growth of superconducting single-crystalline (Lu, Ca) Ba2Cu3O7−δ whiskers

Single-crystalline (Lu, Ca)Ba₂Cu₃O_7−δ (Lu(Ca)123) whiskers have been successfully grown using the Te-doping method. X-ray diffraction patterns of Lu(Ca)123 whiskers showed sharp (0 0 l) peaks corresponding to REBa₂Cu₃O_7−δ phase (RE = rare earth elements). Transport measurements showed that the superconducting transition occurred at 83 K in the obtained whiskers.     

Measurement of the WWγ cross section and direct limits on anomalous quartic gauge boson couplings at LEP

The process e⁺e⁻→W⁺W⁻γ is analysed using the data collected with the L3 detector at LEP at a centre-of-mass energy of 188.6 GeV, corresponding to an integrated luminosity of 176.8 pb⁻¹. Based on a sample of 42 selected W⁺W⁻ candidates containing an isolated hard photon, the W⁺W⁻γ cross section, defined within phase-space cuts, is measured to be: σ_WWγ=290±80±16 fb, consistent with the Standard Model expectation. Including the process , limits are derived on anomalous contributions to the Standard Model quartic vertices W⁺W⁻γγ and W⁺W⁻Zγ at 95% CL: −0.043 GeV⁻²<a₀/Λ²<0.043 GeV⁻², −0.08 GeV⁻²<a_c/Λ²<0.13 GeV⁻², −0.41 GeV⁻²<a_n/Λ²<0.37 GeV⁻².     

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)     

Study on nonlinear optical absorption properties of [(CH3)4N]2[Cu(dmit)2] by Z-scan technique

The third-order optical nonlinearities of an organo-metallic compound, [(CH₃)₄N]₂[Cu(dmit)₂] (dmit²⁻=4,5-dithiolate-1,3-dithiole-2-thione), abbreviated as MeCu, dissolved in acetone are characterized by Z-scan technique with picosecond and nanosecond laser pulses in the near-infrared region. Two-photon absorption has been found when the sample solution is irradiated by 40 ps pulse width at 1064 nm and the two-photon absorption (TPA) coefficient β_TPA is 4×10⁻¹³ m/W. While excited by 15 ns laser pulses at 1053 nm, the Z-scan spectra reveal strong reverse saturable absorption (RSA) and the nonlinear absorption coefficient β_RSA is estimated to be as high as 7.07×10⁻¹¹ m/W which is much larger than β_TPA. An explanation for this enhancement is given. All the results suggest that MeCu may be a promising candidate for the application to optical limiting in the near-infrared region.     

Studies of the quantum Hall to quantum Hall insulator transition in InSb-based 2DESs

The temperature dependence of ρ_xx is studied in the vicinity of the quantum Hall to quantum Hall insulator transition (ν=1→0) in InSb/InAlSb based 2DESs. ρ_xx displays a symmetric temperature dependence about the transition with on the QH side and on the insulating side. A plot of 1/T₀ for successive ν displays power-law divergence with 1/T₀∝|ν−ν_c|^−γ,² with γ=2.2±0.3. This critical behavior in addition to the behavior expected of the quantum transport regime confirms that the QH/QHI transition is indeed a good quantum phase transition.     

Quasi-α-particle mechanism of pion double charge exchange on light nuclei

A microscopic theory of π-meson double charge exchange (DCE) on light nuclei has been suggested and developed on the supposition that the corresponding elementary process proceeds by quasi-α-particle formation within the nucleus. Light nuclei consisting of both α-particles and α-particles and clusters of other kinds are considered. To describe the bound state of the quasi-α- particle and the continuum spectrum state of four identical nucleons, the four-body hyperspherical basis has been applied, while to obtain the wave functions of the centers of mass of the cluster relative motion we solve either the three-body Schrödinger equation (in the case of a three-body cluster configuration) or the two-body Schrödinger equation (in the case of a two-body cluster configuration). The reactions π^± + ¹²C → π + 4p(4n) + 2α, π⁻ + ⁷Li → π⁺ + 4n + ³H, π^± + ⁶Li → π + 4p(4n) + n + p, π^± + ⁶Li → π + 4p(4n) + d are investigated. It is shown that the effect of the final-state interaction between the four nucleons emitted by the nucleus in the process of π-meson DCE is rather important. The available experimental data on the ⁷Li nucleus can be explained quite satisfactorily on the supposition that this nucleus has a two-body cluster structure, and, hence, the π-meson DCE process occurs only on the α-particle.The differential and total cross sections of the reactions under investigation calculated as functions of the incident pion energy are essentially different for different nucleon-nucleon potentials. Experimental study of DCE on α-particle nuclei is shown to be a timely problem.     

Acoustical and excess properties of {1-hexanol + n-hexane, or n-octane, or n-decane} at (298.15, 303.15, and 308.15) K

Densities (ρ) and speeds of sound (u) for the binary mixtures of 1-hexanol with n-hexane, n-octane and n-decane have been measured over the entire composition range at 298.15, 303.15 and 308.15 K. The dynamic viscosities (η) for these systems have been measured at 298.15 K. From experimental data, excess molar volumes (V_m^E), molar isentropic compressibility (K_s,m), excess molar isentropic compressibility (K_s,m^E), deviation in speed of sound (u^D) from their ideal values (u^id) in an ideal mixture, and excess free volumes (V_f^E) have been calculated. The excess functions have also been correlated with the Redlich–Kister polynomial equation. The viscosity data have been analysed in terms of some semi-empirical equations. The theoretical values of speed of sound (u) and isentropic compressibility (κ_S) have also been estimated using the Prigogine–Flory–Patterson (PFP) theory with the van der Waals (vdW) potential energy model and the results have been compared with experimental values. The effect of chain-length of n-alkanes as well as the temperature on the excess properties has also been studied.