Kinetic isotope effects of proton transfer reaction for amines by ultrasonic relaxation methods: Unexpected evidence from the results in ethylamine solutions

Ultrasonic absorption coefficients for ethylamine in heavy water (D2O) and in light water (H2O) have been measured in the frequency range from 0.8 to 220 MHz at 25 degrees C. A single relaxational process has been observed in these two kinds of solutions. From the concentration dependence of the ultrasonic relaxation parameters, and following the reaction mechanism proposed by Eigen et al. for ethylamine in H2O, the causes of the relaxations have been attributed to a perturbation of an equilibrium associated with a deuteron or proton transfer reaction. The rate and equilibrium constants have been estimated from deuterioxide or hydroxide ion concentration dependence of the relaxation frequency, and the kinetic isotope effects have been determined. In addition, the standard volume changes of the reactions have been calculated from the concentration dependence of the maximum absorption per wavelength, and the adiabatic compressibility has also been determined from the density and sound velocity for ethylamine in D2O and in H2O, respectively. These results are compared with those for propylamine and butylamine and are discussed in relation to the different kinetic properties between D2O and H2O, the reaction radii derived by Debye theory, and the structural properties of the reaction intermediate.

Isotope effect in proton-transfer and association-dissociation reactions for butylamine by ultrasonic relaxation methods

Ultrasonic absorption coefficients were measured for butylamine in heavy water (D2O) in the frequency range from 0.8 to 220 MHz and at concentrations from 0.0278 to 2.5170 mol dm(-3) at 25 degrees C; two kinds of relaxation processes were observed. One was found in relatively dilute solutions (up to 0.5 mol dm(-3)), which was attributed to the hydrolysis of butylamine. In order to compare the results, absorption measurements were also carried out in light water (H2O). The rate and thermodynamic parameters were determined from the concentration dependence of the relaxation frequency and the maximum absorption per wavelength. The isotope effects on the diffusion-controlled reaction were estimated and the stability of the intermediate of the hydrolysis was considered while comparing it with the results for propylamine in H2O and D2O. Another relaxation process was observed at concentrations greater than 1 mol dm(-3) in D2O. In order to examine the solution characteristics, proton NMR measurements for butylamine were also carried out in D2O. The chemical shifts for the gamma- and delta-proton in butylamine molecule indicate the existence of an aggregate. From profiles of the concentration dependence of the relaxation frequency and the maximum absorption per wavelength of sound absorption, the source of the relaxation was attributed to an association-dissociation reaction, perhaps, associated with a hydrophobic interaction. The aggregation number, the forward and reverse rate constants and the standard volume change of the reaction were determined. It was concluded from a comparison with the results in H2O that the hydrophobic interaction of butylamine in D2O is stronger than that in H2O. Also, the isotope effect on this reaction was interpreted in terms of the solvent structure.

Ultrasonic relaxation kinetics on fast deuteron transfer reaction

Propylamine has been selected to investigate the isotope effect of a fast deuteron transfer reaction by ultrasonic relaxation method. Ultrasonic absorption coefficients of propylamine in heavy water (D2O) at 25 degrees C in the concentration range from 0.0107 to 0.6300 mol dm(-3) have been measured by pulse and resonance methods over the frequency range from 0.8 to 220 MHz. A Debye-type single relaxation absorption has been observed in the solution. From the dependence of the ultrasonic relaxation parameters on the concentration and solution pH, the source of the observed relaxation has been attributed to a perturbation of the chemical equilibrium associated with the deuteron transfer reaction. The rate and equilibrium constants have been determined by the measurement of the deuteroxyl ion concentration dependence of the relaxation frequency. Also the standard volume change of the reaction has been determined from the concentration dependence of the maximum absorption per wavelength and the adiabatic compressibility has been calculated from the density and the sound velocity in the solution. These results have then been compared with those obtained for propylamine in light water (H2O). The forward rate constant is greater and the reverse rate constant is smaller in DO than in H2O. The standard volume change for deuteron transfer is greater than that for proton transfer reaction, and the adiabatic compressibility shows a similar trend. These data support an argument that there exists a stronger hydrogen bond in D2O than in H2O. The difference of the stability in the intermediate states, R-ND3+... OD- and R-NH3+... OH-, has also been considered from the results of the isotope effects.

Zn-doped InGaAs Base Heterojunction Bipolar Transistors Grown by Low Pressure Metal Organic Chemical Vapor Deposition

High performance InP/InGaAs heterojunction bipolar transistors(HBTs) have been widely used in high-speed electronic devices and optoelectronic integrated circuits. InP-based HBTs were fabricated by low pressure metal organic chemical vapor deposition(MOCVD) and wet chemical etching. The sub-collector and collector were grown at 655 ℃ and other layers at 550 ℃. To suppress the Zn out-diffusion in HBT, base layer was grown with a 16-minute growth interruption. Fabricated HBTs with emitter size of 2.5×20 μm~2 showed current gain of 70~90, breakdown voltage(BV_(CE0))>2 V, cut-off frequency(f_T) of 60 GHz and the maximum relaxation frequency(f_(MAX)) of 70 GHz.

Spin relaxation and dephasing mechanism in (Ga,Mn)As studied by time-resolved Kerr rotation

Spin dynamics in (Ga,Mn)As films grown on GaAs(001) was investigated by Time-resolved magneto-optical Kerr effect. The Kerr signal decay time of (Ga,Mn)As without external magnetic field applied was found to be several hundreds picoseconds, which suggested that photogenerated polarized holes and magnetic ions are coupled as a ferromagnetic system. Nonmonotonic temperature dependence of relaxation and dephasing (R&D) time and Larmor frequency manifests that Bir-Aronov-Pikus mechanism dominates the spin R&D time at low temperature, while D'yakonov-Perel mechanism dominates the spin R&D time at high temperature, and the crossover between the two regimes is Curie temperature.

Dielectric relaxation and giant dielectric constant of Nb-doped CaCu3Ti4O12 ceramics under dc bias voltage

CaCu3Ti(4-x)Nb(x)O(12) (x = 0, 0.01, 0.08, 0.2) ceramics were fabricated by a conventional solid-state reaction method. The ceramics showed the body-centered cubic structure without any foreign phases and the grain size decreases with Nb doping. Two Debye-type relaxations were observed for the Nb-doped samples at low frequency and high frequency, respectively. The complex electric modulus analysis revealed that the surface layer, grains and grain boundaries contributed to the dielectric constant. The low-frequency dielectric constant relative to the surface layer decreased to a minimum and then increased with the dc bias voltage at 100 Hz, which were well explained in terms of a model containing two metal oxide semiconductors in series, confirming the surface layer in the ceramics. The shift voltage V-B corresponding to the minimal capacitance increased with increase of the composition x. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low-frequency noise properties of GaN Schottky barriers deposited on intermediate temperature buffer layers

Metal-semiconductor-metal (MSM) structures were fabricated by RF-plasma-assisted MBE using different buffer layer structures. One type of buffer structure consists of an AlN high-temperature buffer layer (HTBL) and a GaN intermediate temperature buffer layer (ITBL), another buffer structure consists of just a single A IN HTBL. Systematic measurements in the flicker noise and deep level transient Fourier spectroscopy (DLTFS) measurements were used to characterize the defect properties in the films. Both the noise and DLTFS measurements indicate improved properties for devices fabricated with the use of ITBL and is attributed to the relaxation of residue strain in the epitaxial layer during growth process. (C) 2003 Elsevier Ltd. All rights reserved.

Dielectric relaxation of poled polymer DCNP/PMMA

We have prepared the polymer thin films of a 3-(1,1-dicyanothenyl)-1-phenyl-4,5-dihydro-1H-pyrazole (DChTP)/poly (methyl methacrylate) (PMMA) guest-host system by spin coating. In order to investigate their temporal and temperature stability, we have measured their dielectric relaxation spectra including the frequency dependence of the real and imaginary parts of dielectric constants. The investigated frequency ranged from 50 Hz to 10 MHz. The measured temperature range above the glass transition temperature T-g (95 degrees C) of the DCNP/PMMA system was from 95 degrees C to 1250C. By using the Adam-Gibbs model, the temperature dependence of the characteristic time tau above T-g was fitted, and the values of the characteristic times tau below T-g were estimated. The lifetimes of the polymer were evaluated by the Kohlrausch-Williams Watts (KWW) empirical decay model. (C) 2000 Elsevier Science B.V. All rights reserved.

High-frequency ferromagnetic resonance on ultrafine cobalt particles

We report on high-frequency (300-700 GHz) ferromagnetic resonance (HF-FMR) measurements on cobalt superparamagnetic particles with strong uniaxial effective anisotropy. We derive the dynamical susceptibility of the system on the basis of an independent-grain model by using a rectangular approach. Numerical simulations give typical line shapes depending on the anisotropy, the gyromagnetic ratio, and the damping constant. HF-FMR experiments have been performed on two systems of ultrafine cobalt particles of different sizes with a mean number of atoms per particles of 150 +/- 20 and 310 +/- 20. In both systems, the magnetic anisotropy is found to be enhanced compared to the bulk value, and increases as the particle size decreases, in accordance with previous determinations from magnetization measurements. Although no size effect has been observed on the gyromagnetic ratio, the transverse relaxation time is two orders of magnitude smaller than the bulk value indicating strong damping effects, possibly originating from surface spin disorders.

Magnetophonon resonance in the energy relaxation of electrons in a quantum well

The magnetophonon resonance effect in the energy relaxation rate is studied theoretically for a quasi-two-dimensional electron gas in a semiconductor quantum well. An electron-temperature model is adopted to describe the coupled electron-phonon system. The energy relaxation time, derived from the energy relaxation rate, is found to display an oscillatory behavior as the magnetic-field strength changes, and reaches minima when the optical phonon frequency equals integer multiples of the electron cyclotron frequency. The theoretical results are compared with a recent experiment, and a qualitative agreement is found.

Low-frequency noise properties of GaN Schottky barriers deposited on intermediate temperature buffer layers

Metal-semiconductor-metal (MSM) structures were fabricated by RF-plasma-assisted MBE using different buffer layer structures. One type of buffer structure consists of an AlN high-temperature buffer layer (HTBL) and a GaN intermediate temperature buffer layer (ITBL), another buffer structure consists of just a single A IN HTBL. Systematic measurements in the flicker noise and deep level transient Fourier spectroscopy (DLTFS) measurements were used to characterize the defect properties in the films. Both the noise and DLTFS measurements indicate improved properties for devices fabricated with the use of ITBL and is attributed to the relaxation of residue strain in the epitaxial layer during growth process. (C) 2003 Elsevier Ltd. All rights reserved.

Identification of nonlinear dynamic systems: Time-frequency filtering and skeleton curves

The nonlinear behavior varying with the instantaneous response was analyzed through the joint time-frequency analysis method for a class of S. D. O. F nonlinear system. A masking operator an definite regions is defined and two theorems are presented. Based on these, the nonlinear system is modeled with a special time-varying linear one, called the generalized skeleton linear system (GSLS). The frequency skeleton curve and the damping skeleton curve are defined to describe the main feature of the non-linearity as well. Moreover, an identification method is proposed through the skeleton curves and the time-frequency filtering technique.

Dislocation dynamics of strain relaxation in epitaxial layers

Many experimental observations have clearly shown that dislocation interaction plays a crucial role in the kinetics of strain relaxation in epitaxial thin films. A set of evolution equations are presented in this article. The key feature of the equations

Identification of Nonlinear Systems Through Time-Frequency Filtering Technique

In the previous paper, a class of nonlinear system is mapped to a so-called skeleton linear model (SLM) based on the joint time-frequency analysis method. Behavior of the nonlinear system may be indicated quantitatively by the variance of the coefficients of SLM versus its response. Using this model we propose an identification method for nonlinear systems based on nonstationary vibration data in this paper. The key technique in the identification procedure is a time-frequency filtering method by which solution of the SLM is extracted from the response data of the corresponding nonlinear system. Two time-frequency filtering methods are discussed here. One is based on the quadratic time-frequency distribution and its inverse transform, the other is based on the quadratic time-frequency distribution and the wavelet transform. Both numerical examples and an experimental application are given to illustrate the validity of the technique.