Search results for "THERMODYNAMICS"
showing 10 items of 2774 documents
Effects of pressure, temperature and atomic exchanges on phase separation dynamics in Au/Ni(111) surface alloy: Kinetic Monte Carlo study
2015
Abstract Instability of the Au/Ni(111) surface alloy is studied in different CO gas pressure, p , and temperature limits using kinetic Monte Carlo simulations. We analyze the reaction front dynamics and formation of Au clusters using the model which takes into account surface adatom pair and three-body interactions, CO adsorption and desorption, catalytic carbonyl formation reaction, Au and Ni adatom diffusion and their concerted exchange. Variation of interaction parameters allows us to identify three possible reaction front propagation limits with different pressure dependencies: (i) slow channel-like flow in agreement with experimental data [1] (step flow rate, R , increases with p ), (i…
Impact of the synergistic collaboration of oligothiophene bridges and ruthenium complexes on the optical properties of dumbbell-shaped compounds.
2012
The linear and non-linear optical properties of a family of dumbbell-shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2'-bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non-linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties …
Berechnung der viskositätszahl und der diffusionskonstante hochpolymerer stoffe mit hilfe eines stäbchenmodells
1953
Die Viskositatszahl linearer Hochpolymerer wird nach zwei Kugelmodellen und einem Stabchenmodell berechnet. Es zeigt sich, das ein kugelsymmetrischer Korper die Reibungsverhaltnisse geknauelter Fadenmolekule nicht richtig erfassen kann. Auf Grund eines Stabchenmodells, dessen Lange der grosten Ausdehnung des Knauels (1,4 hst) entspricht, wird die Gleichung. abgeleitet, in welcher die Konstante Φ2 den universellen Wert 1,3.1023 besitzt, awahrend Φ1 von speziellen hydrodynamischen Verhaltnissen im Knauel abhangt. Bei hoheren Molekulargewichten ist Φ1 ein annahernd konstanter Bruchteil des 2. Terms, so das die vereinfachte Gleichung mit Φ′ = 1,62.1023 annahernde Gultigkeit besitzt. Die Absolut…
Graphical representation of polynuclear acid-base and complex equilibria.
1983
Abstract A calculation procedure for diagrams of log CM = ƒ(pL) at various values of the ratio of analytical concentrations, CL/CM, in polynuclear binary systems is described. The diagrams are useful in the resolution of analytical problems of practical interest involving acid-base equilibria (such as the preparation of buffer solutions) and complex equilibria. The presence of a solid phase is also considered.
Negative thermal expansion of quartz glass at low temperatures: An ab initio simulation study
2017
Abstract Using a mixed classical Molecular dynamics (MD)/ab initio simulation scheme combined with a quasi-harmonic approximation, we calculate the linear thermal expansion coefficient αL(T) in vitreous silica glasses. The systems are first cooled down by classical MD simulations. Then they are structurally relaxed by ab initio DFT calculations. The vibrational properties are calculated employing the frozen phonon method, and these results are finally used to calculate the Helmholtz free energy as a function of volume. In agreement with experiments, our simulations predict that αL(T) is negative at low temperatures up to T ≈ 150 K. In this low-temperature regime, the simulation results are …
Quantum dynamics of 16O + 36O2 and 18O + 32O2 exchange reactions
2015
We present quantum dynamical investigations of (16)O + (36)O2 and (18)O + (32)O2 exchange reactions using a time-independent quantum mechanical method and an accurate global potential energy surface of ozone [Dawes et al., J. Chem. Phys. 135, 081102 (2011)]. Initial state-selected integral cross sections, rate constants, and Boltzmann averaged thermal rate constants are obtained and compared with earlier experimental and theoretical results. The computed thermal rate constants for the oxygen exchange reactions exhibit a negative temperature dependence, as found experimentally. They are in better agreement with the experiments than the previous studies on the same reactions.
Phase transition kinetics and reorientational dynamics of the plastic crystal meta-carborane studied by deuteron NMR
2002
Meta-carborane shows an orientationally disordered, orthorhombic phase which transforms into an ordered monoclinic phase near 170 K and into a quasi-isotropic cubic phase near 280 K. From deuteron magnetization measurements both transitions are found to exhibit a thermal hysteresis and slow transformation kinetics. Furthermore, solid-echo NMR spectra and spin-lattice relaxation times are reported. These results indicate that in the orthorhombic phase the meta-carborane molecules perform a strongly anisotropic motion which is characterized by a temperature dependent amplitude.
Rotation correlation time as a measure of microviscosity of excited state isomerization reactions of three cyanine dyes in n-alcohol solutions
1994
Abstract Rotation correlation times of three chemically similar cyanine dyes of different sizes in n -alcohol solutions have been recorded at several temperatures by using polarized picosecond spectroscopy. For all three dyes the linear temperature dependencies of τ or on η/ T were observed to be independent of solvent up to viscosities of about 60 cP. The rotational motion of the dyes proceeds at much slower rates than the excited state isomerization in viscous solutions of the same fluidity. Isomerization seems to depend on special solvent-induced changes of the force field of the reactant and clearly proceeds faster, especially for the two larger dyes, than predicted by Kramers' theory a…
Effect of Experimental and Sample Factors on Dehydration Kinetics of Mildronate Dihydrate: Mechanism of Dehydration and Determination of Kinetic Para…
2014
The dehydration kinetics of mildronate dihydrate [3-(1,1,1-trimethylhydrazin-1-ium-2-yl)propionate dihydrate] was analyzed in isothermal and nonisothermal modes. The particle size, sample preparation and storage, sample weight, nitrogen flow rate, relative humidity, and sample history were varied in order to evaluate the effect of these factors and to more accurately interpret the data obtained from such analysis. It was determined that comparable kinetic parameters can be obtained in both isothermal and nonisothermal mode. However, dehydration activation energy values obtained in nonisothermal mode showed variation with conversion degree because of different rate-limiting step energy at hi…
Thermodynamics of the spin transition in [FexZn1−x(2-pic)3]Cl2 · EtOH
1992
Abstract With a new type of calorimeter we reinvestigated the specific heat Cp of the mixed crystals [FexZni1−x(2-pic)3]Cl2 · EtOH in the temperature range from 15 to 300 K. On the basis of a phenomenological thermodynamic model the anomaly in the Cp(T) curve of the mixed crystal (x = 0.73) can be quantitatively described as a result of the spin transition (1A1(low spin, LS) → 5T2(high spin, HS)). The parameters of the Gibbs free energy were independently derived from the temperature dependence of the HS fraction γ in [FexZn1−x(2-pic)3]Cl2 · EtOH. The pure iron complex (x = 1) exhibits a two-step spin transition. In the temperature range between the two steps the entropy obtained from the C…