Search results for "Arrhenius Equation"
showing 10 items of 83 documents
Mössbauer relaxation spectra in arbitrarily ordered absorbers—Line shape analysis for an iron(II) spincrossover complex in the presence of texture
1989
The stochastic theory of Mossbauer line shapes is formulated in a fashion which allows the evaluation of the spectral shapes for absorbers of arbitrary thickness, texture, and an anisotropic Lamb—Mossbauer factor. The results are specialized to a two-state-relaxation model of fluctuating electric hyperfine interaction in the case of an absorber of axially symmetric texture. The formalism is applied to the line shape analysis of Mossbauer spectra of a textured sample of the spin-crossover complex [Fe(mtz)6] (PF6)2 (mtz=1-methyltetrazole). It is found that between 185 and 240 K the rate constants for the HS→LS conversion are temperature independent, whereas an Arrhenius behaviour is found for…
Dynamics of spin state conversion processes in the solid state
1989
High spin (HS) ⇌ low spin (LS) conversions in transition metal complexes are nonradiative transitions between spin states. In this contribution, we present a study of the temperature and pressure dependence of the HS ⇌ LS intersystem crossing dynamics. For some iron(II) spin-crossover complexes, the rate constants were determined by line shape analysis of57Fe Mossbauer spectra. Their temperature dependence is described by an Arrhenius equation, their pressure dependence is interpreted within absolute rate theory. HS → LS conversion rates at low temperatures were determined from the relaxation of light-induced formation of HS states, monitored by optical spectroscopy. Deviations from a simpl…
Intersystem crossing in Fe(II) coordination compounds
1994
Fe(II) spin-crossover systems can be quantitatively converted from the low-spin (LS) to the high-spin (HS) state well below the thermal transition temperature by irradiating either into the metal-ligand charge transfer or d-d absorption bands, and even in low-spin systems a transient population of the HS state can be achieved. This fact can be made use of to determine HS → LS relaxation rate constants for a wide variety of Fe(II) spin-crossover and low-spin systems. The HS → LS relaxation shows strong deviations from an Arrhenius behaviour, with nearly temperature-independent tunnelling below ∼70 K and a thermally activated process above ∼100 K. The range of more than 12 orders of magnitude…
Dipolar and orientational glass formation in two-dimensional films of CO mixtures
2002
Heat-capacity and dielectric measurements have been performed to study orientational and dipolar order and disorder phenomena in submonolayer films of CO and binary mixtures of CO physisorbed on graphite and boron nitride (BN). With both methods transitions to quadrupolar and dipolar ordered low-temperature phases have been found for pure CO. Calorimetric measurements revealed that the dipolar transition of CO on graphite belongs to the universality class of the two-dimensional (2D) Ising model. It will be shown that in dilute mixtures of CO with CH 4 molecules a dramatic suppression of this phase transition occurs. This effect turned out to be much stronger than that previously observed in…
Phonon coupling of non-bridging oxygen hole center with the silica environment: Temperature dependence of the 1.9 eV emission spectra
2008
Abstract We report an experimental study on the shape of the 1.9 eV emission associated with non-bridging oxygen hole centers in silica and its temperature dependence, from 4 up to 300 K, under visible and ultraviolet excitation. Our analysis points out that these defects are coupled with their environment by phonons whose contribution can be described by the single mode of mean frequency between 300–400 cm −1 and Huang–Rhys factor of ∼3. On increasing the temperature, the luminescence intensity undergoes a thermal quenching caused by non-radiative processes, its deviation from a pure Arrhenius law can be accounted for by an uniform distribution of activation energy, from 0.002 to 0.05 eV. …
The effects of Pr3+ doping on the dielectric and photoluminescence properties of BaTi0.9(Yb0.5Nb0.5)0.1O3 ceramic
2019
Abstract The praseodymium Pr3+ doped BaTi0.9(Yb0.5Nb0.5)0.1O3 (BTYN01) ceramic, under low concentration (0.1%), was prepared by a conventional ceramic fabrication technique and its phase structure, microstructure, dielectric, vibrational and photoluminescence (PL) properties was studied. Both X-ray diffraction (XRD) and Raman studies confirmed the incorporation of Pr3+ into A-site lattice of BTYN01. The structure of Ba0.9985Pr0.001□0.0005Ti0.9(Yb0.5Nb0.5)0.1O3 (BTYN01-Pr) shows the coexistence of Pm 3 ¯ m -cubic symmetry (∼10%) and P4mm-tetragonal symmetry (∼90%) at room temperature. The dielectric study reveals that the maximum of the dielectric constant of BTYN01-Pr occurred at 283 K. The…
Irradiation induced Germanium Lone Pair Centers in Ge-doped Sol-gel SiO2: luminescence lifetime and temperature dependence
2010
We studied the temperature dependence of the emission profile and of the lifetime, measured at 4.3 eV, related to the germanium lone pair centers (GLPC) induced by gamma ray at 5 MGy in a Ge-doped silica sample and in an analogous sample irradiated at 10 MGy, in which by a successive thermal treatment up to 415 °C the induced GLPC has been modified (named residual GLPC in the following). The measurements were recorded in the temperature range 10-300 K using an excitation of ∼5.2 eV. The data show that the energy level scheme of the induced and the residual GLPC is very similar to that of the native defects generated during the synthesis, and the intersystem crossing process (ISC) of the ind…
Space-charge relaxation in perovskites.
1994
We report a dielectric anomaly in several perovskites at intermediate frequencies 10\ensuremath{\le}f\ensuremath{\le}${10}^{7}$ Hz in the temperature range 400 \ifmmode^\circ\else\textdegree\fi{}C \ensuremath{\le}T\ensuremath{\le}800 \ifmmode^\circ\else\textdegree\fi{}C. We have found this dielectric maximum in more than 100 samples of various shapes and textures. This anomaly is shown to arise from a Debye dielectric dispersion that slows down following an Arrhenius law. We have established a link between this dielectric relaxation and the conductivity. We propose that it can be achieved through a space-charge model that quantitatively agrees with the experimental results in the lower temp…
Data mining, dashboards and statistics: a powerful framework for the chemical design of molecular nanomagnets
2021
Abstract Three decades of intensive research in molecular nanomagnets have brought the magnetic memory in molecules from liquid helium to liquid nitrogen temperature. The enhancement of this operational temperature relies on a wise choice of the magnetic ion and the coordination environment. However, serendipity, oversimplified theories and chemical intuition have played the main role. In order to establish a powerful framework for statistically driven chemical design, we collected chemical and physical data for lanthanide-based nanomagnets to create a catalogue of over 1400 published experiments, developed an interactive dashboard (SIMDAVIS) to visualise the dataset, and applied inferentia…
Memory effects and coverage dependence of surface diffusion in a model adsorption system
1999
We study the coverage dependence of surface diffusion coefficients for a strongly interacting adsorption system O/W(110) via Monte Carlo simulations of a lattice-gas model. In particular, we consider the nature and emergence of memory effects as contained in the corresponding correlation factors in tracer and collective diffusion. We show that memory effects can be very pronounced deep inside the ordered phases and in regions close to first and second order phase transition boundaries. Particular attention is paid to the details of the time dependence of memory effects. The memory effect in tracer diffusion is found to decay following a power law after an initial transient period. This beha…