Search results for "Metastability"
showing 10 items of 262 documents
Cavitation in 3He-4he Liquid Mixtures
2002
Phase transitions under equilibrium conditions are experimentally well determined and take place in the coexistence regime. However, phase transitions do not always occur under equilibrium conditions. As the new phase forms, the free energy of the system is lowered, but the original phase can be held in a metastable state close to the equilibrium transition point. Although they are internally stable, in each case there exists another configuration that has a lower thermodynamical potential. The metastable state is separated from the stable state by a thermodynamic barrier. Due to statistical fluctuations in density or concentration, this barrier can be overcome as the result of the formatio…
Lattice dynamics of zircon-type NdVO4 and scheelite-type PrVO4 under high-pressure
2021
Abstract Zircon-type NdVO4 and scheelite-type PrVO4 have been studied by means of Raman spectroscopy up to approximately 20 GPa. In the first compound, zircon-scheelite and scheelite-fergusonite phase transitions are reported at 6.4(3) and 19.6(4) GPa, respectively. In the case of scheelite-type PrVO4, a reversible phase transition to a PbWO4-III structure is observed at 16.8(5) GPa. In both cases, a scheelite-type structure is recovered in a metastable state at low pressures. The pressure evolution of the Raman modes is also reported. Our experimental findings are supported by ab initio calculations, which allowed us to discuss the role of mechanic and dynamical instabilities in the phase …
Kinetic behaviour of a structural phase transition in Langmuir-Blodgett multilayers studied by energy dispersive x-ray reflectivity
1992
Various multilayers of Cd stearate were prepared by means of the Langmuir-Blodgett technique and investigated at T = Ts - ΔT (Ts, melting point of LB film). The x-ray scattering spectrum was recorded in several time intervals using an energy dispersive set up. For ΔT = 3 ... 9 K the observed intensity reduction of Bragg peaks, which corresponds to the multilayer periodicity, is recorded as a function of time. In addition new peaks appear. This is interpreted in terms of a kinetically driven phase separation of the metastable LB-phase. The time needed for phase disorder and the nucleation of the new phase decreases for smaller ΔT. The measured layer spacing of the new phase is larger than th…
Pressure dependence of photoluminescence of InAs/InP self-assembled quantum wires
2007
6 páginas, 4 figuras, 1 tabla.-- PACS 62.50.+ p, 73.21.Hb, 78.55.Cr, 78.67.Lt, 81.15.Hi, 81.16.Dn
High-Spin → Low-Spin Relaxation in [Fe(bpp)2](CF3SO3)2 H2O after LIESST and Thermal Spin-State Trapping—Dynamics of Spin Transition Versus Dynamics o…
1996
The iron(II) complex [Fe(bpp)2]-(CF3SO3)2 H2O (bpp = 2,6-bis(pyrazolyl-3-yl)pyridine) shows a thermal spin transition associated with a hysteresis of approximately 140 K width. The transition temperatures T1/2 (where the fraction of HS species γHS = 0.5) are 147 K and ≈285 K in the cooling and heating directions, respectively. The compound shows the LIESST and reverse-LIESST effects at low temperatures. The relaxation of the metastable HS states generated by LIESST was observed quantitatively at temperatures between 77.5 and 85 K by Mossbauer spectroscopy. Metastable HS states can also be generated by rapid cooling of the sample. The relaxation of the metastable HS states formed by thermal …
Double-well thermodynamic potentials and spinodal curves: how real are they?
2007
The concept of double-well thermodynamic potentials, ubiquitous since the van der Waals description of the vapour-to-liquid transition and the Landau theory of phase transitions, is critically re-examined. Particular emphasis is put on the extent to which spinodal curves (separating ‘metastable’ from ‘unstable’ states) are meaningful. It is argued that in full thermodynamic equilibrium spinodals are well-defined when one either considers finite subsystems of an infinitely large system, or systems with all linear dimensions finite. Evidence is given that in a finite (cubic) d-dimensional box the spinodals correspond (in a fluid) to the rounded ‘droplet evaporation’ or ‘bubble condensation’ t…
Luminescence-detected EPR of oxygen-fluorine vacancy complexes in CaF2
2009
In several CaF2 single crystals grown by the Bridgman method and doped with CaO or in addition with SrF2 or NaF a luminescence band between 470 nm and 600 nm could be excited at 212 nm, its peak wavelength depending on the doping. With photo-luminescence (PL) detected EPR five spin triplet centres were identified. Their axial fine structure constants D varied from 87 mT to 690 mT whereby the most intense spectra had the smallest D value. Theoretical calculations of the fine structure tensors and superhyperfine interactions show that the most intense and probable triplet centre consists of a pair of an OF– on a F– site next to a nearest neighbour F– vacancy which, compared to the well-known …
Modification of vacuum-ultraviolet absorption of SiOH groups in SiO2 glass with temperature, F2 laser irradiation, and H–D isotope exchange
2006
Abstract Variations of vacuum-ultraviolet (VUV) absorption of silanol (SiOH) groups in synthetic wet SiO 2 glass with temperature, exposure to F 2 laser light, and with H–D isotope exchange were examined at photon energies below 8 eV. The intensity of the VUV absorption band decreases with cooling or with exposure to F 2 laser light. The spectral changes in both cases are qualitatively similar and are attributed to an alternation of the bonding configuration of SiOH groups from isolated into hydrogen-bonded states. However, the resultant states are distinctly different: the hydrogen-bonded state formed on cooling is restored reversibly to the isolated state on heating, while that induced by…
Effects induced by UV laser radiation on the blue luminescence of silica nanoparticles
2013
The effects induced on the blue luminescence centered around 2.8 eV, characteristic of silica nanoparticles, were investigated by monitoring its intensity during and after exposure to the third and the fourth harmonic of a Nd:YAG pulsed laser. The luminescence trend is found to be dependent on the UV photon energy: 3.50 eV photons induce a partial bleaching followed by a recovery in the post-irradiation stage; 4.66 eV photons cause a total bleaching permanent after the irradiation. These results are interpreted as the conversion of luminescent defects towards stable and metastable configurations.
Extension of the Launay Quantum Reactive Scattering Code and Direct Computation of Time Delays.
2019
Scattering computations, particularly within the realm of molecular physics, have seen an increase in study since the development of powerful quantum methods. These dynamical processes can be analyzed via (among other quantities) the duration of the collision process and the lifetime of the intermediate complex. We use the Smith matrix Q = -iℏS†dS/dE calculated from the scattering matrix S and its derivative with respect to the total energy. Its real part contains the state-to-state time delays, and its eigenvalues give the lifetimes of the metastable states [ Smith Phys. Rev. 1960 , 118 , 349 - 356 ]. We propose an extension of the Launay HYP3D code [ Launay and Le Dourneuf Chem. Phys. Let…