Temperature dependence of g values in tetragonal ionic Cu++ salts

A temperature dependence has been observed in the spin-Hamiltonian parameters of the Cu++ ion in a tetragonal crystal field and the variation has been interpreted in terms of vibronic effects.

Thermal conductivity of liquids and its temperature dependence

The temperature dependence of thermal conductivity of liquids as given by Horrocks and McLaughlin is re-examined and useful relations to estimate thermal conductivity are presented. In the case of the 12 homologous series considered the maximum deviation is about 5%.

On The Temperature-Dependence of Regioselectivity in the Amination of Bromobenzotropones

The ipso/cine ratio in the amination of 5-bromo-2,3-benzo- or 2-bromo-4,5-benzotropone shows a dependence upon the temperature at which the reaction is conducted, changing in favour of the ipso-product when the temperature is maintained high, ruling out an aryne-type mechanism. A comparison of independent mechanisms envisaged for the formation of the two isomeric products suggests a two-part reason: (i) at a higher reaction temperature, C-protonation, a step necessary for the formation of the cine-product, could be retarded when a direct internal mode is interfered with by a less efficient external one, and (ii) reketonisation by elimination of bromide, needed to form the ipso-product, is likely to have a high temperature coefficient enabling the rate of its formation to overtake that of the cine-product.

Temperature dependence of hydrogen evolution reaction on nickel oxide electrode in sealed nickel/cadmium cells

The impedance of sealed nickel/cadmium cells around a cell e.m.f. of 0.0 V was measured at five different temperatures between � 10 and +30 °C. The results show that the behaviour is similar at all temperatures. Based on the experimental results, the relation between charge-transfer resistance (Rct) and temperature (T) has been established for the Volmer reaction. Further, the value of cathodic transfer coefficient (?) has been estimated.

Reactions of cyanogen radical with alkanes and an explanation for negative temperature dependence of rate constants

Reactions of cyanide radicals with alkanes have been investigated by ab initio methods. It is found that the potential energy surface for reaction of CN with a primary C-H bond in methane has a small positive barrier while reactions of CN with a secondary and a tertiary C-H bond in alkanes are barrierless at the correlated level. A simple explanation for the obtained negative temperature dependence of rate constants for reactions of CN with a secondary and a tertiary C-H bond in alkanes are given in terms of the collision theory of bimolecular reactions. It is shown that for barrierless reactions the negative temperature dependence of the rate constants is attributed to the variation of the pre-exponential factor with temperature.

Limiting ionic conductance of symmetrical, rigid ions in aqueous solutions: Temperature dependence and solvent isotope effects

Limiting ionic conductance (Lambda(0)) of rigid symmetrical unipositive ions in aqueous solution shows a strong temperature dependence. For example, Lambda(0) more than doubles when the temperature is increased from 283 to 318 K. A marked variation also occurs when the solvent is changed from ordinary water (H2O) to heavy water (D2O). In addition, Lambda(0) shows a nonmonotonic size dependence with a skewed maximum near Cs+. Although these important results have been known for a long time, no satisfactory theoretical explanation exists for these results. In this article we present a simple molecular theory which provides a nearly quantitative explanation in terms of microscopic structure and dynamics of the solvent. A notable feature of this theory is that it does not invoke any nonquantifiable models involving solvent-berg or clatherates. We find the strong temperature dependence of Lambda(0) to arise from a rather large number of microscopic factors, each providing a small but nontrivial contribution, but all acting surprisingly in the same direction. This work, we believe, provides, for the first time, a satisfactory explanation of both the anomalous size and temperature dependencies of Lambda(0) of unipositive ions in molecular terms. The marked change in Lambda(0) as the solvent is changed from H2O to D2O is found to arise partly from a change in the dielectric relaxation and partly from a change in the effective interaction of the ion with the solvent.

Temperature dependence of non-Debye disorder in doped manganites

Ca-doped manganite La1-xCaxMnO3 samples with x=0.2 and 0.4 were investigated by extended x-ray absorption fine structure (EXAFS) as a function of temperature and preparation method. The samples exhibit characteristic resistivity change across the metal-insulator (MI) transition temperature whose shape and position depend on Ca-doping concentration and sample thermal treatment. EXAFS results evidenced an increase of nonthermal disorder at the MI transition temperature which is significantly correlated with the resistivity behavior.

Temperature dependence of the levitation effect - Implications for separation of multicomponent mixtures

Sufficiently long molecular dynamics simulations have been carried out on spherical monatomic sorbates in NaY zeolite, interacting via simple Lennard-Jones potentials, to investigate the dependence of the levitation effect on the temperature. Simulations carried out in the range 100-300 K suggest that the anomalous peak in the diffusion coefficient (observed when the levitation parameter, gamma, is near unity) decreases in intensity with increase in temperature. The rate of cage-to-cage migrations also exhibits a similar trend. The activation energy obtained from Arrhenius plots is found to exhibit a minimum when the diffusion coefficient is a maximum, corresponding to the gamma approximate to 1 sorbate diameter. In the linear or normal regime, the activation energy increases with increase in sorbate diameter until it shows a sharp decrease in the anomalous regime. Locations and energies of the adsorption sites and their dependence on the sorbate size gives interesting insight into the nature of the underlying potential-energy surface and further explain the observed trend in the activation energy with sorbate size. Cage residence times, tau(c), show little or no change with temperature for the sorbate with diameter corresponding to gamma approximate to 1, whereas there is a significant decrease in tau(c) with increase in temperature for sorbates in the linear regime. The implications of the present study for the separation of mixtures of sorbates are discussed.

Temperature dependence study of chlorine NQR frequency and spin-lattice relaxation time in 2-amino,-3,5-dichloropyridine

Chlorine-35 NQR frequency and spin-lattice relaxation time measurements as a function of temperature in the range 77-300 K were carried out on 2-amino-3,5-dichloropyridine. Two NQR signals were observed and were assigned to the two chlorines present in the molecule using the additive model for substituent effects. The temperature dependence of the NQR frequency was analysed in terms of the torsional oscillations of the molecule and the torsional frequencies and their temperature dependence were calculated numerically using a two-mode approximation. The temperature dependence of the NQR spin-lattice relaxation time was found to be mainly due to the torsional oscillations of the molecule, with anharmonicity effects showing up at higher temperatures. Copyright (C) 1999 John Wiley & Sons, Ltd.

Temperature dependence of infrared and Raman modes in polymeric RbC60

Temperature dependence of the intra-molecular vibrational modes Of C-60 in the quasi-1D polymeric RbC60, across the low temperature transition at similar to50 K, has been probed through infrared (IR) and Raman spectroscopies. With the lowering of temperature, the split IR modes of RbC60 are seen to harden but below 50 K a small but definitive signature of an anomalous softening is observed. In addition, the background IR transmission shows an increase below 50 K with the opening of a well defined gap in the electronic spectrum. The implications of these results, along with those of Raman measurements, are discussed in terms of the interaction of intra-molecular phonons with electrons and spin excitations in the system. (C) 2002 Published by Elsevier Science Ltd.

Anomalous Temperature dependence of Fermi-edge Singularity in Modulation-doped AlGaAs/InGaAs/GaAs hetero-structures

The temperature and power dependence of Fermi-edge singularity (FES) in high-density two-dimensional electron gas, specific to pseudomorphic AlxGa1-xAs/InyGa1-yAs/GaAs heterostructures is studied by photoluminescence (PL). In all these structures, there are two prominent transitions E11 and E21 considered to be the result of electron-hole recombination from first and second electron sub-bands with that of first heavy-hole sub-band. FES is observed approximately 5 -10 meV below the E21 transition. At 4.2 K, FES appears as a lower energy shoulder to the E21 transition. The PL intensity of all the three transitions E11, FES and E21 grows linearly with excitation power. However, we observe anomalous behavior of FES with temperature. While PL intensity of E11 and E21 decrease with increasing temperature, FES transition becomes stronger initially and then quenches-off slowly (till 40K). Though it appears as a distinct peak at about 20 K, its maximum is around 7 - 13 K.

Anomalous temperature dependence of phonons and photoluminescence bands in pyrochlore Er(2)Ti(2)O(7): signatures of structural deformation at 130 K

We report a Raman study of single crystal pyrochlore Er(2)Ti(2)O(7) as a function of temperature from 12 to 300 K. In addition to the phonons, various photoluminescence (PL) lines of Er(3+) in the visible range are also observed. Our Raman data show an anomalous red-shift of two phonons (one at similar to 200 cm(-1) and another at similar to 520 cm(-1)) upon cooling from room temperature which is attributed to phonon-phonon anharmonic interactions. However, the phonons at similar to 310, 330, and 690 cm(-1) initially show a blue-shift upon cooling from room temperature down to about 130 K, followed by a red-shift, indicating a structural deformation at similar to 130 K. The intensities of the PL bands associated with the transitions between the various levels of the ground state manifold ((4)I(15/2)) and the (2)H(11/2) as well as (4)S(3/2) excited state manifolds of Er(3+) show a change at similar to 130 K. Moreover, the temperature dependence of the peak position of the two PL bands shows a change in their slope (d(omega)/d(T)) at similar to 130 K, thus further strengthening the proposal of a structural deformation. The temperature dependence of the peak positions of the PL bands has been analyzed using the theory of optical dephasing in crystals.

Temperature dependence of the energy gap and free carrier absorption in bulk InAs0.05Sb0.95 single crystals

Temperature dependence of the energy gap and free carrier absorption in a high-quality InAs0.05Sb0.95 single crystal was studied between 90 K and 430 K through the absorption spectra. At this alloy concentration, the room-temperature energy gap was measured to be 0.15 eV. Varshni- and the Bose–Einstein-type fit parameters were obtained from the measured temperature dependence of the energy gap, and the latter gave the zero-temperature gap to be 0.214 eV. It was found that although Weider’s empirical formula for the dependence of the energy gap on temperature and the alloy concentration agrees with the value of the gap at room temperature, it is inaccurate in describing its temperature dependence. From the free carrier absorption measurements, the phonon limited cross section of 7.35×10−16 cm2 at 15 μm was deduced at room temperature.