Evaluation of solute-solvent interactions from solvent blue-shifts of n → π* transitions of C=O, C=S, NO2 and N=N groups: hydrogen bond energies of various donor-acceptor systems

Effects of non-polar, polar and proton-donating solvents on the n → π* transitions of C=O, C=S, NO2 and N=N groups have been investigated. The shifts of the absorption maxima in non-polar and polar solvents have been related to the electrostatic interactions between solute and solvent molecules, by employing the theory of McRAE. In solvents which can donate protons the solvent shifts are mainly determined by solute-solvent hydrogen bonding. Isobestic points have been found in the n → π* bonds of ethylenetrithio-carbonate in heptane-alcohol and heptane-chloroform solvent systems, indicating the existence of equilibria between the hydrogen bonded and the free species of the solute. Among the different proton-donating solvents studied water produces the largest blue-shifts. The blue-shifts in alcohols decrease in the order 2,2,2-trifluoroethanol, methanol, ethanol, isopropanol and t-butanol, the blue-shift in trifluoroethanol being nearly equal to that in water. This trend is exactly opposite to that for the self-association of alcohols. It is suggested that electron-withdrawing groups not merely decrease the extent of self-association of alcohols, but also increase the ability to donate hydrogen bonds. The approximate hydrogen-bond energies for several donor-acceptor systems have been estimated. In a series of aliphatio ketones and nitro compounds studied, the blue-shifts and consequently the hydrogen bond energies decrease with the decrease in the electron-withdrawing power of the alkyl groups. It is felt that electron-withdrawing groups render the chromophores better proton acceptors, and the alcohols better donors. A linear relationship between n → π* transition frequency and the infrared frequency of ethylenetrithiocarbonate has been found. It is concluded that stabilization of the electronic ground states of solute molecules by electrostatic and/or hydrogen-bond interactions determines the solvent shifts.

Clustering and solute-vacancy binding energies in Al-4.4% Zn alloy with 0.01% ternary additions

Isochronal and isothermal ageing experiments have been carried out to determine the influence of 0.01 at. % addition of a second solute on the clustering rate in the quenched Al-4,4 a/o Zn alloy. The influence of quenching and ageing temperatures has been interpreted to obtain the apparent vacancy formation and vacancy migration energies in the various ternary alloys. Using a vacancy-aided clustering model the following values of binding free energy have been evaluated: Ce-0.18; Dy-0.24; Fe-0.18; Li-0.25; Mn-0.27; Nb-0.18; Pt-0.23; Sb-0.21; Si-0.30; Y-0.25; and Yb-0.23 (± 0.02 eV). These binding energy values refer to that between a solute atom and a single vacancy. The values of vacancy migration energy (c. 0.4 eV) and the experimental activation energy for solute diffusion (c. 1.1 eV) are unaffected by the presence of the ternary atoms in the Al-Zn alloy.

Shell-model calculation of defect energies in alkali halides employing crystal-independent interionic potential parameters

Shell model calculation of defect energies in alkali halides have been carried out using the ion-dependent, crystal-independent potential parameters of Sangster and Atwood (1978). Results indicate that appreciable differences exist between barrier heights for migration of cations and anions. While barrier heights for cations are generally lower than for anions in alkali halides of NaCl structure, the opposite is true in alkali halides of CsCl structure.

A numerical survey of relativistic rotating neutron star structures using the Hartle-Thorne formalism

A broad numerical survey of relativistic rotating neutron star structures was compiled using an exhaustive list of presently available equation of state models for neutron star matter. The structure parameters (spherical deformations in mass and radii, the moment of inertia and quadrupole moment, oblateness, and free precession) are calculated using the formalism proposed by Hartle and Thorne (1968). The results are discussed in relation to the relevant observational information. Binary pulsar data and X-ray burst sources provide information on the bulk properties of neutron stars, enabling the derivation of constraints that can be put on the structure of neutron stars and equation of state models.

Standard Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5

The Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5 from component oxides have been measured using solid state galvanic cells incorporating CaF2 as the solid electrolyte under pure oxygen at a pressure of 1.01 x 10(5) Pa Because the superconducting compound YBa2Cu3O7-delta coexists with any two of the phases CuO, BaCuO2 and Y2BaCuO5, the data on BaCuO2 and Y2BaCuO5 obtained in this study provide the basis for the evaluation of the Gibbs' energy of formation of the 1-2-3 compound at high temperatures.

Excitation and relaxation energies of trans-stilbene: Confined singlet, triplet, and charged bipolarons

The π-electronic excitations and excited-state geometries of trans-stilbene (tS) are found by combining exact solutions of the Pariser-Parr-Pople (PPP) model and semiempirical Parametric Method 3 (PM3) calculations. Comprehensive comparisons with tS spectra are obtained and related to the fluorescence and topological alternation of poly(paraphenylenevinylene) (PPV). The one-photon absorption and triplet of tS correspond, respectively, to singlet and triplet bipolarons confined to two phenyls, while the tS2- ground state is a confined charged bipolaron. Independent estimates of the relaxation energy between vertical and adiabatic excitation show the bipolaron binding energy to depend on both charge and spin, as expected for interacting π electrons in correlated or molecular states. Complete configuration interaction within the PPP model of tS accounts for the singlet-triplet gap, for the fine-structure constants and triplet-triplet spectra, for two-photon transitions and intensities, and for one-photon spectra and the radiative lifetime, although the relative position of nearly degenerate covalent and ionic singlets is not resolved. The planar PM3 geometry and low rotational barrier of tS agree with resolved rotational and vibrational spectra in molecular beams. PM3 excitation and relaxation energies for tS bipolarons are consistent with experiment and with PPP results. Instead of the exciton model, we interpret tS excitations in terms of states that are localized on each ring or extended over an alternating chain, as found exactly in Hückel theory, and find nearly degenerate transitions between extended and localized states in the singlet, triplet, and dianion manifolds. The large topological alternation of the extended system increases the ionicity and interchanges the order of the lowest one- and two-photon absorption of PPV relative to polyenes.

Phase relations in the systems Cu–O–R2O3(R = Tm, Lu) and Gibbs energies of formation of Cu2R2O5 compounds

The phase relations in the systems Cu–O–R2O3(R = Tm, Lu) have been determined at 1273 K by X-ray diffraction, optical microscopy and electron probe microanalysis of samples equilibrated in evacuated quartz ampules and in pure oxygen. Only ternary compounds of the type Cu2R2O5 were found to be stable. The standard Gibbs energies of formation of the compounds have been measured using solid-state galvanic cells of the type, Pt|Cu2O + Cu2R2O5+ R2O3‖(Y2O3)ZrO2‖CuO + Cu2O‖Pt in the temperature range 950–1325 K. The standard Gibbs energy changes associated with the formation of Cu2R2O5 compounds from their binary component oxides are: 2CuO(s)+ Tm2O3(s)→Cu2Tm2O5(s), ΔG°=(10400 – 14.0 T/K)± 100 J mol–1, 2CuO(s)+ Lu2O3(s)→Cu2Lu2O5(s), ΔG°=(10210 – 14.4 T/K)± 100 J mol–1 Since the formation is endothermic, the compounds become thermodynamically unstable with respect to component oxides at low temperatures, Cu2Tm2O5 below 743 K and Cu2Lu2O5 below 709 K. When the chemical potential of oxygen over the Cu2R2O5 compounds is lowered, they decompose according to the reaction, 2Cu2R2O5(s)→2R2O3(s)+ 2Cu2O(s)+ O2(g) The equilibrium oxygen potential corresponding to this reaction is obtained from the emf. Oxygen potential diagrams for the Cu–O–R2O3 systems at 1273 K are presented.

Generalised one-dimensional burgers'equation in relativistic fluiddynamics

This work deals with the effects of weak nonlinearity and weak dissipation on a linear wave in relativistic gasdynamics. Using perturbation and asymptotic expansions, a relativistic analogue of generalised one-dimensional Burgers' equation of classical gasdynamics is derived to describe far-field description of the wave. Steady state solution is presented for strict one-dimensional case.

Phase relations and gibbs energies in the system Mn-Rh-O

Phase relations in the system Mn-Rh-O are established at 1273 K by equilibrating different compositions either in evacuated quartz ampules or in pure oxygen at a pressure of 1.01 x 10(5) Pa. The quenched samples are examined by optical microscopy, X-ray diffraction, and energy-dispersive X-ray analysis (EDAX). The alloys and intermetallics in the binary Mn-Rh system are found to be in equilibrium with MnO. There is only one ternary compound, MnRh2O4, with normal spinel structure in the system. The compound Mn3O4 has a tetragonal structure at 1273 K. A solid solution is formed between MnRh2O4 and Mn3O4. The solid solution has the cubic structure over a large range of composition and coexists with metallic rhodium. The partial pressure of oxygen corresponding to this two-phase equilibrium is measured as a function of the composition of the spinel solid solution and temperature. A new solid-state cell, with three separate electrode compartments, is designed to measure accurately the chemical potential of oxygen in the two-phase mixture, Rh + Mn3-2xRh2xO4, which has 1 degree of freedom at constant temperature. From the electromotive force (emf), thermodynamic mixing properties of the Mn3O4-MnRh2O4 solid solution and Gibbs energy of formation of MnRh2O4 are deduced. The activities exhibit negative deviations from Raoult's law for most of the composition range, except near Mn3O4, where a two-phase region exists. In the cubic phase, the entropy of mixing of the two Rh3+ and Mn3+ ions on the octahedral site of the spinel is ideal, and the enthalpy of mixing is positive and symmetric with respect to composition. For the formation of the spinel (sp) from component oxides with rock salt (rs) and orthorhombic (orth) structures according to the reaction, MnO (rs) + Rh2O3 (orth) --> MnRh2O4 (sp), DELTAG-degrees = -49,680 + 1.56T (+/-500) J mol-1. The oxygen potentials corresponding to MnO + Mn3O4 and Rh + Rh2O3 equilibria are also obtained from potentiometric measurements on galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte. From these results, an oxygen potential diagram for the ternary system is developed.

Gibbs energies of formation of chromium carbides

The carbon potentials corresponding to the two-phase mixtures Cr + Cr23C6, Cr23C6 + Cr7C3, and Cr7C3 + Cr3C2 in the binary system Cr-C were measured in the temperature range 973 to 1173 K by using the methane-hydrogen gas equilibration technique. Special precautions were taken to prevent oxidation of the samples and to minimize thermal segregation in the gas phase. The standard Gibbs energies of formation of Cr23C6, Cr7C3, and Cr3C2 were derived from the measured carbon potentials. These values are compared with those reported in the literature. The Gibbs energies obtained in this study agree well with those obtained from solid-state cells incorporating CaF2 and ThO2(Y2O3) as solid electrolytes and sealed capsule isopiestic measurements reported in the literature.

Gibbs energies of formation of UMoC1.7 and UMoC2

The chemical potentials oi carbon associated with two three-phase fields in the system U-Mo-C were measured by using the methane-hydrogen gas equilibration technique in the temperature range 973 to 1173K. The technique was validated by measuring the standard Gibbs energy of formation of Mo2C. From the experimentally measured values of the chemical potential of carbon in the ternary phase fields UC+Mo+UMoC1.7 and UC+UMoC1.7+UMoC2 and data for UC from the literature, the Gibbs energies of formation of the two ternary carbides were derived:

Phase equilibria in the system CaO-CoO-SiO2 and Gibbs energies of formation of the quaternary oxides CaCoSi2O6, Ca2CoSi2O7, and CaCoSiO4

Phase relations in the pseudoternary system CaO-CoO-SiO2 have been established at 1323 K. Three quaternary oxides were found to be stable: CaCoSi2O6 with clinopyroxene (Cpx), Ca2CoSi2O7 with melilite (Mel), and CaCoSiO4 with olivine (Ol) structures. The Gibbs energies of formation of the quaternary oxides from their component binary oxides were measured using solid-state galvanic cells incorporating yttria-stabilized zirconia as the solid electrolyte in the temperature range of 1000-1324 K. The results can be summarized as follows: CoO (rs) + CaO (rs) + 2SiO(2) (Qtz) --> CaCoSi2O6 (Cpx), Delta G(f)(0) = -117920 + 11.26T (+/-150) J/mol CoO (rs) + 2CaO (rs) + 2SiO(2) (Qtz) --> Ca2CoSi2O7 (Mel), Delta G(f)(0) = -192690 + 2.38T (+/-130) J/mol CoO (rs) + CaO (rs) + SiO2 (Qtz) --> CaCoSiO2 (Ol), Delta G(f)(0) = -100325 + 2.55T (+/-100) J/mol where rs = rock salt (NaCl) structure and Qtz = quartz. The uncertainty limits correspond to twice the standard error estimate. The experimentally observed miscibility gaps along the joins CaO-CoO and CaCoSiO4-Co2SiO4 were used to calculate the excess free energies of mixing for the solid solutions CaxCo1-xO and (CayCo1-y)CoSiO4:Delta G(E) = X(1 - X)[31975X + 26736 (1 - X)] J/mol and Delta G(E) = 23100 (+/-250) Y(1 - Y) J/mol. A T-X phase diagram for the binary CaO-CoO was computed from the thermodynamic information; the diagram agrees with information available in the literature. The computed miscibility gap along the CaCoSiO4-Co2SiO4 join is associated with a critical temperature of 1389 (+/-15) K. Stability fields for the various solid solutions and the quaternary compounds are depicted on chemical-potential diagrams for SiO2, CaO, and CoO at 1323 K.

Some aspects of the solitary waves in a relativistic inhomogeneous plasma

In contrast to earlier observations on various solitary wave propagations, especially those bifurcated by the compressive and rarefactive solitary waves, the existence of spiky and explosive solitary waves is here believed to arise because of the presence of free and trapped electrons. So far, very few studies have been carried out to satisfactorily explain the presence of the solitary waves in space as observed by satellites. It is also attempted to highlight the probable impact on the various solitary wave propagations in a generalized multi-component, inhomogeneous plasma upon consideration of a relativistic treatment. It is expected that such a treatment will prove the existence of the solitary waves most expeditiously and exhibit the presence of chaos therein, thus giving a suitable explanation to the observations of various forms of spiky and explosive solitary waves in space-plasma. Copyright (C) 1996 Elsevier Science Ltd