Search results for "METASTABILITY"
showing 10 items of 262 documents
Self-assembly of a bioelastomeric structure: solution dynamics and the spinodal and coacervation lines.
1990
The stability, metastability, and instability regions of aqueous solutions of a representative synthetic bioelastomeric polymer, poly (Val-Pro-Gly-Val-Gly), were determined by a combined use of elastic and quasi-elastic light scattering experiments. The approach followed here offers the attractive advantage of singling out the relevant contributions to the total scattering even in the presence of traces of noninteracting larger sized impurities. Conclusions so reached were checked by means of independent experiments. The present results provide descriptions of the very early events in the physics of bioelastogenesis in terms of general polymer science and phase transitions, and in terms of …
Ultrafast Photo-Dynamics of a Reversible Photochromic Spiropyran
2002
We report the first ultrafast ring closure kinetics of the merocyanine (MC) of a reverse photochromic spiropyran 1‘,3‘,3‘-trimethyl-6,8-dinitrospiro[2H-1-benzopyran-2,2-indoline] (6,8-dinitro BIPS) and its 1‘-(2-carboxyethyl) substituted derivative. The reaction is fast and essentially over in a few hundred picoseconds. The rate of MC-S1 state decay evaluated from transient absorbance can be correlated directly with the MC-S1 state lifetime as determined using stimulated and ordinary emission measurements. The recovery of the MC-S0 state from MC-S1 has a component with a lifetime of 60−78 ps in acetonitrile with a second component of 350−470 ps probably due to a metastable intermediate. We …
Critical temperature of the LIESST effect in iron(II) spin crossover compounds
1999
Abstract The light-induced crossover in a series of iron(II) compounds has been investigated by irradiating the sample at 10 K with a Kr + laser coupled to an optical fiber within a SQUID cavity. The temperature dependence of the molar fraction of the light-induced metastable HS state has been recorded for 22 compounds. The critical LIESST temperature, T c (LIESST), has been defined as the temperature for which the light-induced HS information was erased in the SQUID cavity. The dependence of T c (LIESST) as a function of the thermal spin crossover temperature, T 1/2 , has been discussed. The effect of cooperation has been analyzed and the influence of horizontal and vertical displacements …
Stability measures in metastable states with Gaussian colored noise
2009
We present a study of the escape time from a metastable state of an overdamped Brownian particle, in the presence of colored noise generated by Ornstein-Uhlenbeck process. We analyze the role of the correlation time on the enhancement of the mean first passage time through a potential barrier and on the behavior of the mean growth rate coefficient as a function of the noise intensity. We observe the noise enhanced stability effect for all the initial unstable states used, and for all values of the correlation time $\tau_c$ investigated. We can distinguish two dynamical regimes characterized by weak and strong correlated noise respectively, depending on the value of $\tau_c$ with respect to …
Noise-enhanced stability of periodically driven metastable states
2000
We study the effect of noise-enhanced stability of periodically driven metastable states in a system described by piecewise linear potential. We find that the growing of the average escape time with the intensity of the noise is depending on the initial condition of the system. We analytically obtain the condition for the noise enhanced stability effect and verify it by numerical simulations.
Signatures of noise-enhanced stability in metastable state
2005
The lifetime of a metastable state in the transient dynamics of an overdamped Brownian particle is analyzed, both in terms of the mean first passage time and by means of the mean growth rate coefficient. Both quantities feature non monotonic behaviors as a function of the noise intensity, and are independent signatures of the noise enhanced stability effect. They can therefore be alternatively used to evaluate and estimate the presence of this phenomenon, which characterizes metastability in nonlinear physical systems.
Escape from a metastable state with fluctuating barrier
2003
Abstract We investigate the escape of a Brownian particle from fluctuating metastable states. We find the conditions for the noise enhanced stability (NES) effect for periodical driving force. We obtain general equations useful to calculate the average escape time for randomly switching potential profiles. For piece-wise linear potential profile we reveal the noise enhanced stability (NES) effect, when the height of “reverse” potential barrier of metastable state is comparatively small. We obtain analytically the condition for the NES phenomenon and the average escape time as a function of parameters, which characterize the potential and the driving dichotomous noise.
Escape Times in Fluctuating Metastable Potential and Acceleration of Diffusion in Periodic Fluctuating Potentials
2004
The problems of escape from metastable state in randomly flipping potential and of diffusion in fast fluctuating periodic potentials are considered. For the overdamped Brownian particle moving in a piecewise linear dichotomously fluctuating metastable potential we obtain the mean first-passage time (MFPT) as a function of the potential parameters, the noise intensity and the mean rate of switchings of the dichotomous noise. We find noise enhanced stability (NES) phenomenon in the system investigated and the parameter region of the fluctuating potential where the effect can be observed. For the diffusion of the overdamped Brownian particle in a fast fluctuating symmetric periodic potential w…
Mass spectra of methoxychlorobenzenes (chloroanisoles)
1988
Electron impact mass of all 19 ring-substituted chloroanisoles have been investigated. The fragmentation pathways were elucidated with the aid of the 1st field-free region metastable ions. The greatest disparity between the spectra of the positional isomers is shown with the [M−CH 3 ] + and [M−CH 2 O] +• ions, i.e., the ortho and para isomers preferentially lose • CH 3 , whereas the meta isomers generally show both loss of • CH 3 and elimination of formaldehyde, the latter process being more dominant with the meta-monochloro and di- and trichloro isomers having two meta-chlorine atoms. Characteristic for all isomers is also the abundant M +• and [M−CH 3 −CO] + ions, the other fragmentation …
Exceedingly Fast Oxygen Atom Transfer to Olefins via a Catalytically Competent Nonheme Iron Species
2016
El mateix article està publicat en alemany a l'edició alemanya d' 'Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2016, vol. 128, núm. 21, p.6418–6422. DOI http://dx.doi.org/10.1002/ange.201601396 The reaction of [Fe(CF3SO3)2(PyNMe3)] with excess peracetic acid at −40 °C leads to the accumulation of a metastable compound that exists as a pair of electromeric species, [FeIII(OOAc)(PyNMe3)]2+ and [FeV(O)(OAc)(PyNMe3)]2+, in fast equilibrium. Stopped-flow UV/Vis analysis confirmed that oxygen atom transfer (OAT) from these electromeric species to olefinic substrates is exceedingly fast, forming epoxides with stereoretention. The impact of the electronic and steric properties of the subs…