scholarly journals A Study of Anonic Motions in Solid Rubidiumand Cesium Tetrachloroaurates(III)by Measuring the Temperature Dependence of Chlorine Nuclear Quadrupolar Relaxation Times

1989 ◽  
Vol 44 (2) ◽  
pp. 125-130 ◽  
Author(s):  
Atsushi Ishikawa ◽  
Tetsuo Asaji ◽  
Daiyu Nakamura ◽  
Ryuichi Ikeda
Keyword(s):  
Temperature Dependence ◽  
Complex Anion ◽  
Lattice Vibration ◽  
Relaxation Times ◽  
Potential Wells ◽  
Square Planar ◽  
Temperature Dependences ◽  
Cesium Salts ◽  
Quadrupolar Relaxation ◽  
Diagonal Axis

Abstract The temperature dependences of 35Cl NQR frequencies and 35Cl nuclear quadrupolar relaxation times T1Q and T2Q were determined above 82K for Rb[AuCl4] and CsfAuClJ up to ca. 340 and 320 K, respectively. Below these temperatures two 35Cl NQR frequencies were observed for each complex whereas no resonance could be detected above the respective temperatures. For both complexes, T1Q observed below ca. 270 K was interpreted as mainly determined by the rotary lattice vibration around the pseudo-C4(C4) axis and each Cl-Au-Cl diagonal axis of the square planar complex anion, whereas T1q observed above ca. 270 K was definitely shown to be determined through the reorientation of the anions about their C′4 axis. The activation energies for the C′4 reorientation of the anions was evaluated to be 71 and 53 kJ mol-1 for the rubidium and cesium salts, respectively. The anionic dynamics are discussed by assuming the motion of the anions within and out of the C4 potential wells at lower and higher temperatures, respectively.

Temperature Dependences in the O + OH → O2 + H Reaction. Quasiclassical Trajectory Calculation

1993 ◽  
Vol 58 (2) ◽  
pp. 234-243 ◽  
Author(s):  
Viliam Klimo ◽  
Martina Bittererová ◽  
Stanislav Biskupič ◽  
Ján Urban ◽  
Miroslav Micov
Keyword(s):  
Temperature Dependence ◽  
Energy Surface ◽  
Analytical Form ◽  
Mean Values ◽  
Quantum Numbers ◽  
Mean Lifetime ◽  
Temperature Dependences ◽  
Quasiclassical Trajectory Calculation ◽  
The Mean ◽  
Combustion Processes

The reaction O + OH → O2 + H in conditions of combustion of hydrocarbons and polymers was modelled by using the method of quasiclassical trajectories. The potential energy surface was determined by the multiconfiguration interaction method and fitted with the analytical form of the extended LEPS function. Attention was paid to the mean values of the vibrational and rotational quantum numbers of O2 molecules and their temperature dependence. The temperature dependence of the mean lifetime of the OOH collision complex was also examined. The calculated rate constants were analyzed and compared with the experimental data over the temperature region of the combustion processes.

The Urbach Rule for the Sodium- and Potassium-Halides

1974 ◽  
Vol 29 (1) ◽  
pp. 145-157 ◽  
Author(s):  
Tetsuhiko Tomiki ◽  
Takeo Miyata ◽  
Hirokazu Tsukamoto
Keyword(s):  
Temperature Dependence ◽  
Acoustic Phonon ◽  
Frequency Factor ◽  
Host Lattice ◽  
Exciton Peak ◽  
Urbach Rule ◽  
Temperature Dependences ◽  
Hole Band ◽  
Sodium And Potassium ◽  
Potassium Halides

Phenomenological and physical aspects of the intrinsic tail spectra of the alkalihalides are studied referring to the new results on the intrinsic tail spectra of KBr and KI and to the temperature dependences of the lowest-energy Γ-exciton peak of the sodium- and potassium-halides. Systematically analysing the temperature dependence of the steepness parameter σs (T) of the Urbach rule for these halides, it is found that the frequency factor has the value nearly equal to the acoustic phonon energy at X or L of each host lattice and the steepness constant σs0 becomes larger in passing from fluoride to iodide. This halogen dependence of σs0 is discussed in terms of the hole band-mass of the Γ8-level.

Bonded Hydrogen and Trapped H2 in a-Si1−xGex:H Alloys

1989 ◽  
Vol 149 ◽  
Author(s):  
E. J. Vanderheiden ◽  
G. A. Williams ◽  
P. C. Taylor ◽  
F. Finger ◽  
W. Fuhs
Keyword(s):  
Temperature Dependence ◽  
Molecular Hydrogen ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Spin Lattice ◽  
H Nmr ◽  
Local Environments

ABSTRACT1H NMR has been employed to study the local environments of bonded hydrogen and trapped molecular hydrogen (H2) in a series of a-Si1−xGex:H alloys. There is a monotonic decrease of bonded hydrogen with increasing x from ≈ 10 at. % at x = 0 (a-Si:H) to ≈ 1 at. % at x = 1 (a-Ge:H). The amplitude of the broad 1H NMR line, which is attributed to clustered bonded hydrogen, decreases continuously across the system. The amplitude of the narrow 1H NMR line, which is attributed to bonded hydrogen essentially randomly distributed in the films, decreases as x increases from 0 to ≈ 0.2. From x = 0.2 to x ≈ 0.6 the amplitude of the narrow 1H NMR line is essentially constant, and for x ≥ 0.6 the amplitude decreases once again. The existence of trapped H2 molecules is inferred indirectly by their influence on the temperature dependence of the spin-lattice relaxation times, T1. Through T1, measurements it is determined that the trapped H2 concentration drops precipitously between x = 0.1 and x = 0.2, but is fairly constant for 0.2 ≤ x ≤ 0.6. For a-Si:H (x = 0) the H2 concentration is ≈ 0.1 at. %, while for x ≥ 0.2 the concentration of H2 is ≤ 0.02 at. %.

Temperature Dependence of Dynamic Properties of Elastomers. Relaxation Distributions

1952 ◽  
Vol 25 (4) ◽  
pp. 720-729 ◽  
Author(s):  
John D. Ferry ◽  
Edwin R. Fitzgerald ◽  
Lester D. Grandine ◽  
Malcolm L. Williams
Keyword(s):  
Distribution Function ◽  
Temperature Dependence ◽  
Dynamic Properties ◽  
Relaxation Times ◽  
Dynamic Mechanical Properties ◽  
Relaxation Processes ◽  
The Real ◽  
Reduced Frequency ◽  
Dynamic Rigidity ◽  
Composite Curve

Abstract By the use of reduced variables, the temperature dependence and frequency dependence of dynamic mechanical properties of rubberlike materials can be interrelated without any arbitrary assumptions about the functional form of either The definitions of the reduced variables are based on some simple assumptions regarding the nature of relaxation processes. The real part of the reduced dynamic rigidity, plotted against the reduced frequency, gives a single composite curve for data over wide ranges of frequency and temperature; this is true also for the imaginary part of the rigidity or the dynamic viscosity. The real and imaginary parts of the rigidity, although independent measurements, are interrelated through the distribution function of relaxation times, and this relation provides a check on experimental results. First and second approximation methods of calculating the distribution function from dynamic data are given. The use of the distribution function to predict various types of time-dependent mechanical behavior is illustrated.

scholarly journals The role of enzyme dynamics and tunnelling in catalysing hydride transfer: studies of distal mutants of dihydrofolate reductase

2006 ◽  
Vol 361 (1472) ◽  
pp. 1307-1315 ◽  
Author(s):  
Lin Wang ◽  
Nina M Goodey ◽  
Stephen J Benkovic ◽  
Amnon Kohen
Keyword(s):  
Temperature Dependence ◽  
Dihydrofolate Reductase ◽  
Isotope Effects ◽  
Hydride Transfer ◽  
Activation Parameters ◽  
Physical Nature ◽  
Enzyme Dynamics ◽  
Temperature Dependences ◽  
Donor Acceptor ◽  
Significant Temperature

Residues M42 and G121 of Escherichia coli dihydrofolate reductase ( ec DHFR) are on opposite sides of the catalytic centre (15 and 19 Å away from it, respectively). Theoretical studies have suggested that these distal residues might be part of a dynamics network coupled to the reaction catalysed at the active site. The ec DHFR mutant G121V has been extensively studied and appeared to have a significant effect on rate, but only a mild effect on the nature of H-transfer. The present work examines the effect of M42W on the physical nature of the catalysed hydride transfer step. Intrinsic kinetic isotope effects (KIEs), their temperature dependence and activation parameters were studied. The findings presented here are in accordance with the environmentally coupled hydrogen tunnelling. In contrast to the wild-type (WT), fluctuations of the donor–acceptor distance were required, leading to a significant temperature dependence of KIEs and deflated intercepts. A comparison of M42W and G121V to the WT enzyme revealed that the reduced rates, the inflated primary KIEs and their temperature dependences resulted from an imperfect potential surface pre-arrangement relative to the WT enzyme. Apparently, the coupling of the enzyme's dynamics to the reaction coordinate was altered by the mutation, supporting the models in which dynamics of the whole protein is coupled to its catalysed chemistry.

Temperature dependence of heats of vaporization, saturated vapour pressures and cohesive energies for a group of amines

1979 ◽  
Vol 44 (12) ◽  
pp. 3521-3528 ◽  
Author(s):  
Vladimír Majer ◽  
Václav Svoboda ◽  
Josef Koubek ◽  
Jiří Pick
Keyword(s):  
Temperature Dependence ◽  
Saturated Vapour ◽  
Temperature Dependences ◽  
Experimental Values ◽  
Cohesive Energies ◽  
Heats Of Vaporization

The temperature dependences of heats of vaporization of propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, cyclohexylamine, diethylamine and triethylamine and saturated vapour pressures of butylamine, isobutylamine, sec-butylamine and triethylamine were measured. The cohesive energies of amines studied in dependence on temperature were calculated from the experimental values.

scholarly journals Temperature dependence of the dielectric function and critical points of α-SnS from 27 to 350 K

2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Hoang Tung Nguyen ◽  
Van Long Le ◽  
Thi Minh Hai Nguyen ◽  
Tae Jung Kim ◽  
Xuan Au Nguyen ◽  
...  
Keyword(s):  
Low Temperature ◽  
Temperature Dependence ◽  
Dielectric Function ◽  
Spectral Energy ◽  
Phonon Interaction ◽  
Electron Phonon Interaction ◽  
Temperature Dependences ◽  
Exciton Effect ◽  
Bose Einstein ◽  
Temperature Gradient Method

Abstract We report the temperature dependence of the dielectric function ε = ε1 + iε2 and critical point (CP) energies of biaxial α-SnS in the spectral energy region from 0.74 to 6.42 eV and temperatures from 27 to 350 K using spectroscopic ellipsometry. Bulk SnS was grown by temperature gradient method. Dielectric response functions were obtained using multilayer calculations to remove artifacts due to surface roughness. We observe sharpening and blue-shifting of CPs with decreasing temperature. A strong exciton effect is detected only in the armchair direction at low temperature. New CPs are observed at low temperature that cannot be detected at room temperature. The temperature dependences of the CP energies were determined by fitting the data to the phenomenological expression that contains the Bose–Einstein statistical factor and the temperature coefficient for describing the electron–phonon interaction.

Monte Carlo simulations of long-range order kinetics in B2 phases

1995 ◽  
Vol 10 (3) ◽  
pp. 591-595 ◽  
Author(s):  
K. Yaldram ◽  
V. Pierron-Bohnes ◽  
M.C. Cadeville ◽  
M.A. Khan
Keyword(s):  
Monte Carlo ◽  
Monte Carlo Simulations ◽  
Nearest Neighbor ◽  
Vacancy Concentration ◽  
Relaxation Times ◽  
Nearest Neighbors ◽  
Migration Energy ◽  
Ordering Kinetics ◽  
Migration Barriers ◽  
Temperature Dependences

The thermodynamic parameters that drive the atomic migration in B2 alloys are studied using Monte-Carlo simulations. The model is based on a vacancy jump mechanism between nearest neighbor sites, with a constant vacancy concentration. The ordering energy is described through an Ising Hamiltonian with interaction potentials between first and second nearest neighbors. Different migration barriers are introduced fur A and B atoms. The results of the simulations compare very well with those of experiments. The ordering kinetics are well described by exponential-like behaviors with two relaxation times whose temperature dependences are Arrhenius laws yielding effective migration energies. The ordering energy contributes significantly to the total migration energy.

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