Highly Asymmetric Electrolytes in the Associative Mean-Spherical Approximation

The associate mean-spherical approximation (AMSA) is used to derive the closed-form expressions for the thermodynamic properties of an (n+m)-component mixture of sticky charged hard spheres, with m components representing polyions and n components representing counterions. The present version of the AMSA explicitly takes into account association effects due to the high asymmetry in charge and size of the ions, assuming that counterions bind to only one polyion, while the polyions can bind to an arbitrary number of counterions. Within this formalism an extension of the Ebeling–Grigo choice for the association constant is proposed. The derived equations apply to an arbitrary number of components; however, the numerical results for thermodynamic properties presented here are obtained for a system containing one counterion and one macroion (1+1 component) species only. In our calculation the ions are pictured as charged spheres of different sizes (primitive model) embedded in a dielectric continuum. Asymmetries in charge of –10:+1, –10:+2, –20:+1, and –20:+2 and asymmetries in diameter of 2:0.4nm and 3:0.4nm are studied. Monte Carlo simulations are performed for the same model solution. By comparison with new and existing computer simulations it is demonstrated that the present version of the AMSA provides semiquantitative or better predictions for the excess internal energy and osmotic coefficient in the range of parameters where the regular hypernetted chain (HNC) and improved (associative) HNC do not yield convergent solutions. The AMSA liquid–gas phase diagram in the limit of complete association (infinitely strong sticky interaction) is calculated for models with different degrees of asymmetry.     

CNDO studies of Y-Ba-Cu-O superconductors V. Co/Cu substitution

Electronic properties of [Co _n Cu_3–n O₁₂]^–17 and [Ba₈Co _n Cu_3–n O₁₂]^–1 model clusters (n=0–3) are investigated using CNDO molecular orbital method. Our results well reproduce the trends of experimental data on Cu-O bond lengths and supposed negative charge transfer from central Cu(1)O chains to lateral Cu(2)O₂ planes with increasing Co content.     

Far-infrared spectrum of excited torsional states of C-13 methanol

The torsion-rotation structure of the far-infrared (FIR) spectrum of the C-13 isotopic species of methyl alcohol has been investigated by high-resolution Fourier transform spectroscopy in the 25–350 cm^–1 region, with emphasis on subbands involving excited torsional states. In this study, 89 such subbands have been identified, with torsional states fromn=1 ton=3 included. As well, a further 4 assignments have been added to our previous work on then=0 ground torsional state. The subband origins together with known microwave results have been fitted by least-squares to our torsion-rotation Hamiltonian, and improved molecular structural and torsional constants for the vibrational ground state are reported. Tables of state-specific constants representing the three leading terms in aJ(J+1) power-series expansion of the torsion-rotation energy levels are given for torsional statesn=0 to 3 and rotationalK values from 0 to 16.     

A New Way of Solving the Wheeler–DeWitt Equation as Applied to Point Sources

A new way of solving the Wheeler–DeWitt equation is proposed which is based on quantization over free parameters of metrics satisfying the Einstein equations. This technique is applied to two point sources described in the classical case by the Tangherlini metric (in an n-dimensional space) and the Reissner–Nordström metric (in the case of the presence of a charge). The results obtained clarify the sense of the Wheeler hypothesis about statistical weights of small dimensionalities and make possible a new approach to the problem of variation of fundamental constants.     

Optical properties of MnAl films

The optical properties of MnAl films of different compositions, deposited at different substrate temperatures and in the thickness range 25 to 90 nm, are reported. The reflectance and transmittance are measured in the wavelength range 320–900 nm for near normal incidence of light. These measurements are used to calculate the optical constants namely, refractive index (n) and extinction coefficient (k). The wavelength and thickness dependence of these optical constants are reported. The optical measurements for films with higher Mn content and grown at higher substrate temperature reveal that n and k values are constant over a wide wavelength range (500–900 nm) showing high reflectance in the visible and near infrared region.     

Calculation of interplanar distances near the faces of ionic crystals with lattices of NaCl type and face-centered molecular crystals

Conclusions Interplanar distances near faces have been calculated for ideal ionic crystals of NaCl type and face-centered molecular crystals by successive approximation [4]. The repulsive forces for the ionic crystals were taken as br^–n, while the attractive and repulsive forces for the molecular crystals were taken asar^–m and br^–n, respectively. The numerical values fora and b were derived from the equilibrium conditions for an infinite crystal.We found that the difference between the interplanar distance and the lattice constant increased as n decreased for ionic crystals, the distance between the second and third planes being the largest.The above difference is positive for molecular crystals and decreases inwards; it is 5% of the lattice constant for the first and second planes but only 0.1% for the fifth and sixth.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 148–150, February, 1972.     

The microwave spectrum, structure, chlorine nuclear quadrupole coupling constants, dipole moment, and centrifugal distortion constants of dichlorosilane

The microwave spectra of three isotopic species of dichlorosilane, SiH₂Cl₂, in its ground vibrational state, have been measured in the frequency region 8–40 GHz. The spectra have yielded values for the rotational constants, centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants, as well as the molecular dipole moment, 1.13 ± 0.02 D. The molecule has C_2v symmetry, and the bond lengths and angles r(Si---Cl=2.033±Å, r(Si---H)=1.480±0.015Å, (Cl---Si---Cl)=109°43′±20±, (H---Si---H)=111°18′±40′ The centrifugal distortion constants have been compared with those calculated using a published force field.     

Molecular simulation of sodium butyl benzene sulfonate at air–water interface and in aqueous solution

Molecular mechanics(MM) calculations for interfacial behaviour of sodium n-butyl benzene sulfonate (NaNBBS), sodium iso-butyl benzene sulfonate (NaIBBS) and sodium tert-butyl benzene sulfonate (NaTBBS) show a significant effect of the butyl group geometry on the surface area occupied by these molecules at the air–water interface. NaNBBS, in comparison with NaIBBS and NaTBBS, shows a closer molecular packing at the interface. The simulation predicts minimum hydrotrope concentration of each hydrotrope to reach surface saturation and molecular surface area at the interface match with good accuracy. The shape, size and charge of the hydrotrope aggregates obtained by molecular dynamics simulation also match well with the results of small angle neutron scattering experiments on the same hydrotrope. The simulation shows non-regular and ellipsoidal hydrotropes aggregates with substantial charge on the surface. The aggregates are also more open structures as compared to surfactant micelles. The water accessible surface area of a NaNBBS aggregate was 25% lower in comparison to that of NaTBBS aggregate, indicating closer packing of NaNBBS molecules. The fractional charge on the NaNBBS aggregate decreases with the increase in the number of NaNBBS molecules in the aggregate indicating more counter-ion association.     

The chemical hardness of molecules and the band gap of solids within charge equilibration formalisms

This work finds that different charge equilibration methods lead to qualitatively different responses of molecules and solids to an excess charge. The investigated approaches are the regular charge equilibration (QE), the atom-atom-charge transfer (AACT), and the split-charge equilibration (SQE) method. In QE, the hardness of molecules and the band gap of solids approaches zero at large particle numbers, affirming the claim that QE induces metallic behavior. AACT suffers from producing negative values of the hardness; moreover valence and conduction bands of solids cross. In contrast to these methods, SQE can reproduce the generic behavior of dielectric molecules or solids. Moreover, first quantitative results for the NaCl molecule are promising. The results derived in this work may have beneficial implications for the modeling of redox reactions. They reveal that by introducing formal oxidation states into force field-based simulations it will become possible to simulate redox reactions including non-equilibrium contact electrification, voltage-driven charging of galvanic cells, and the formation of zwitterionic molecules.     

Calculation of the cubic symmetry force constants of methyl bromide and methyl chloride

The cubic symmetry force constants have been calculated for methyl bromide and methyl chloride through the method developed by Hoy et al. (Mol. Phys. 24, 1265–1290 (1972)). The spectroscopic constants recently reported in the literature have been utilized for the present analysis. Out of a total of 38 independent cubic force constants, 6 and 10 constants were constrained to zero for a methyl bromide and methyl chloride, respectively, in which a diagonal force constant of F₆₆₆ was included for both molecules. However, it is noted that those force constants which are only concerned with the A₁ symmetry coordinates have been determined independent of the constraint for both of these molecules.     

Semiclassical laser theory in the stochastic and thermodynamic frameworks

The thermodynamic properties of the laser distribution in the steadily oscillating state are investigated to determine the minimum characteristic of the entropy production. First, the laser Langevin equation for five random variables is treated in the light of the stochastic calculus to deduce the photon-number rate equationn = – C+(n – n_c) + [A/(1 + sn)](n–n_A), where n_n and n₄ are the two constants of the fluctuation attributed to the noise forces subject to the usual fluctuation-dissipation theorem, withn ₄ < 0 for the inverted atomic population. We then combine the dynamics of the lasing mode with a model open system of the Lebowitz type with two reservoirs for which the entropy production(p) is expressed and made subject to a variational principle: The modified variation scheme, the same as Prigogine's local potential method, is shown to give the exact lasing distributionp as the optimum between two distributions of thermal type with temperatures far from each other.     

Macroscopic and microscopic parameters of laser dye solvents: m-xylene and dioxane

For the laser designer and other users the optical, electrical and refractive parameters have been obtained for pure nonpolar laser dye solvents m-xylene and dioxane. The refractive index (n) and its thermo-optic constant (dn/dT) at argon laser wavelength 514.5 nm and He–Ne laser wavelength 632.8 nm, are measured. The values of n and dn/dT are used to calculate the optical permittivity ε=n² and its variation with temperature dε/dT. Applying Cauchy's equation the optical and dielectric dispersion (dn/dλ and dε/dλ) are determined. The variation of −dn/dT, −dε/dT, molar refractivity and thermal volume expansion coefficient as a function of wavelength are calculated and represented. Furthermore Cauchy's constants A and B as a function of temperature are plotted. The specific and molar refractivities, specific and molar dispersivity total polarizability, distortion polarizability, ratio of atomic to electronic polarizability, molecular radius, relaxation time, electric susceptibility characteristic impedance, and other physical parameters were calculated. Additionally, density, thermal linear expansion coefficient and molar polarization as a function of temperature were calculated at the laser wavelengths 514.5 nm.     

Accurate Measurement of Small Spin–Spin Couplings in Partially Aligned Molecules Using a Novel J-Mismatch Compensated Spin-State-Selection Filter

The accurate measurement of small spin–spin coupling constants in macromolecules dissolved in a liquid crystalline phase is important in the context of molecular structure investigation by modern liquid state NMR. A new spin-state-selection filter, DIPSAP, is presented with significantly reduced sensitivity to J-mismatch of the filter delays compared to previously proposed pulse sequences. DIPSAP presents an attractive new approach for the accurate measurement of small spin–spin coupling constants in molecules dissolved in anisotropic solution. Application to the measurement of ¹⁵N–¹³C′ and ¹H^N–¹³C′ coupling constants in the peptide planes of ¹³C, ¹⁵N labeled proteins demonstrates the high accuracy obtained by a DIPSAP-based experiment.     

Crystal chemistry of the Tl2−xBa2Ca n Cu n+1O2n+6 (n=0, 1, 2) high-T c superconductors

We report on a comparative crystal chemical study of the Tl_2–xBa₂Ca _n Cu _n+1O_2n+6(n=0, 1, 2) high-T _c superconductors. Superconducting properties were determined by DC-conductivity and-susceptibility measurements. An X-ray diffraction analysis reveals the nonstoichiometry of the compounds as a link between structural and superconducting behavior. A comparison of the different structures gives evidence that T1 deficiency in the TlO double layers increases with increasingn; this deficiency causes apparent Cu valences larger than 2+in the superconducting phases thus maintaining the charge balance. By extracting appropriate chemical formulas and performing a bond strength calculation we obtained the mixed-valent oxidation state of copper for the superconducting tetragonal phases as being 2.17+(n=0), 2.25+(n=1) and 2.31+(n=2) respectively; for the non-superconducting orthorhombic phase Tl_2–xBa₂CuO_6–y a Cu valence of about 2+is suggested.     

Reactive molecular dynamic simulations of hydrocarbon dissociations on Ni(111) surfaces

Empirical potential parameters for H, C and Ni elements have been developed for the ReaxFF force field in order to study the decomposition of small hydrocarbon molecules on nickel using molecular dynamics simulations. These parameters were optimized using the geometrical and energetic information obtained from density functional (DFT) calculations on a subset of hydrogen and methane reactions with nickel (111) surfaces. The resulting force field was then used to obtain a molecular perspective of the dynamics of the methane dissociative adsorption on Ni(111) as well as two other small alkane molecules, ethane and n-butane. NVT simulations of dissociative adsorption of methane over a range of temperatures enabled the estimation of the sticking coefficient for the adsorption as well as the activation energy of the first C–H bond breaking. The rate constants of each elementary step (both forward and reverse) of CH_x dissociation on Ni(111) were obtained by monitoring the surface species and a microkinetic model was constructed as a result. Qualitative analyses of the simulations of ethane and n-butane decompositions on Ni(111) demonstrate that such reactive MD technique can also be used to obtain useful information on complex reaction networks.     

Classical Electromagnetism and the Aharonov–Bohm Phase Shift

Although there is good experimental evidence for the Aharonov–Bohm phase shift occurring when a solenoid is placed between the beams forming a double-slit electron interference pattern, there has been very little analysis of the relevant classical electromagnetic forces. These forces between a point charge and a solenoid involve subtle relativistic effects of order v ² /c ² analogous to those discussed by Coleman and Van Vleck in their treatment of the Shockley–James paradox. In this article we show that a treatment exactly analogous to that given by Coleman and Van Vleck predicts classical electromagnetic forces which provide the basis for the Aharonov–Bohm phase shift. The magnetic force on the solenoid due to the passing charge leads to a displacement of the solenoid center of energy which must be balanced by the displacement of the passing charge. This classical displacement of the passing charge is exactly what is required to account for the Aharonov–Bohm phase shift. Also, we discuss a magnetic moment model which appears frequently in the literature and note that although the model provides conservation of linear momentum, it does not satisfy the general requirements for relativistic theories. We give an example suggesting that the new equation of motion for a magnetic moment proposed by Aharonov, Pearle, and Vaidman based upon the hidden momentum of the magnetic moment is completely inappropriate. Finally, we emphasize that the Aharonov–Casher phase shift is also explained by classical electromagnetic forces exactly parallel to those explaining the Aharonov–Bohm phase shift.     

Guided propagation in a step-index, multi-mode fiber: effect of index difference variation on allowable TM propagation constants

The effect of variation of core and cladding index difference, Δn=n_core−n_cladding, on allowable values for the guided mode transverse magnetic propagation constants within a step-index, multi-mode optical fiber is investigated. We use a iterative computational technique to calculate the propagation constants for modes inside and outside the core that satisfy the boundary conditions contained within the characteristic eigen-equation for the TM field components. Evidence of a strong dependence of the allowable propagation constants on changes of Δn is shown.     

Internal rotation and chlorine nuclear quadrupole coupling of o-chlorotoluene studied by microwave spectroscopy and ab initio calculations

The microwave spectrum of o-chlorotoluene has been reinvestigated using molecular beam Fourier transform microwave (MB-FTMW) spectrometers in the frequency range of 4–23 GHz. Due to the high resolution of this molecular beam technique the analysis yielded improved rotational constants, centrifugal distortion constants, and, for the first time, the complete chlorine nuclear quadrupole coupling tensor. From the torsional fine structure the barrier to internal rotation of the methyl group was found to be 5.5798(52) kJ mol⁻¹. Experimental results and ab initio calculations are compared.     

The rotational spectrum of acrylonitrile in excited states of the two low-frequency CCN bending vibrational modes

The strongest vibrational satellites in the rotational spectrum of acrylonitrile have been assigned and frequencies of μ_a- and μ_b-type transitions in the frequency range 27–184 GHz are reported for the first two excited states in the lowest frequency in-plane CCN bending vibrational mode and the first excited state in the out-of-plane CCN bending mode. The values of the rotational constants, the quartic and sextic centrifugal distortion constants, and one octic centrifugal distortion constant are determined for each of these states. Less extensive results are also presented for the third quantum of the in-plane bend. The data set for the ground state has been extended by a number of new measurements and the improved ground state constants are used in a discussion of changes in rotational and centrifugal distortion constants with vibrational state where all constants associated with P_zⁿ and P²P_z⁽ⁿ⁻²⁾ terms in the Hamiltonian are found to reflect the common origin of the two CCN bends.