Effects of initial height on the steady-state persistence probability of linear growth models

The effects of the initial height on the temporal persistence probability of steady-state height fluctuations in up-down symmetric linear models of surface growth are investigated. We study the (1 + 1)-dimensional Family model and the (1 + 1)-and (2 + 1)-dimensional larger curvature (LC) model. Both the Family and LC models have up-down symmetry, so the positive and negative persistence probabilities in the steady state, averaged over all values of the initial height h(0), are equal to each other. However, these two probabilities are not equal if one considers a fixed nonzero value of h(0). Plots of the positive persistence probability for negative initial height versus time exhibit power-law behavior if the magnitude of the initial height is larger than the interface width at saturation. By symmetry, the negative persistence probability for positive initial height also exhibits the same behavior. The persistence exponent that describes this power-law decay decreases as the magnitude of the initial height is increased. The dependence of the persistence probability on the initial height, the system size, and the discrete sampling time is found to exhibit scaling behavior.

Si nanowire growth on sapphire: Classical incubation, reverse reaction, and steady state supersaturation

Si nanowire growth on sapphire substrates by the vapor-liquid-solid (VLS) method using Au catalyst particles has been studied. Sapphire was chosen as the substrate to ensure that the vapor phase is the only source of Si. Three hitherto unreported observations are described. First, an incubation period of 120-480 s, which is shown to be the incubation period as defined in classical nucleation theory, is reported. This incubation period permits the determination of a desolvation energy of Si from Au-Si alloys of 15 kT. Two, transmission electron microscopy studies of incubation, point to Si loss by reverse reaction as an important part of the mechanism of Si nanowire growth by VLS. Three, calculations using these physico-chemical parameters determined from incubation and measured steady state growth rates of Si nanowires show that wire growth happens from a supersaturated catalyst droplet. (C) 2015 AIP Publishing LLC.

Accurate Steady-State Representation of a Doubly Fed Induction Machine

This letter presents an accurate steady-state phasor model for a doubly fed induction machine. The drawback of existing steady-state phasor model is discussed. In particular, the inconsistency of existing equivalent model with respect to reactive power flows when operated at supersynchronous speeds is highlighted. Relevant mathematical basis for the proposed model is presented and its validity is illustrated on a 2-MW doubly fed induction machine.

Alternate Proof for Steady-State Equivalent Circuit of a Doubly Fed Induction Machine

This letter presents an alternate proof for the steady-state equivalent circuit of a doubly fed induction machine operating at supersynchronous speeds. The spatial orientation of rotating magnetic fields is used to validate the conjugation of rotor side quantities arising in supersynchronous mode. The equivalent circuit is further validated using dynamic simulations of a stand-alone machine.

Electronic absorption and emission spectroscopic investigations of the interaction of the fullerenes, C60 and C70, with amines and aromatic molecules

Electronic absorption spectroscopy and fluorescence spectroscopy have been used to investigate the interaction of the fullerenes C60 and C70 with diethylaniline, and with aromatic solvents such as benzene. C60 interacts weakly with aromatic amines in the ground state while C70 does not interact at all. Steady state fluorescence emission and lifetime measurements show that both C60 and C70 form excited state complexes (exciplexes) with the amines in non-aromatic solvents such as methylcyclohexane, but not in benzene. In benzene, only fluorescence quenching is observed due to the interaction between the π systems of the aromatic solvent and the fullerene in the ground state. This is also borne out by the systematic study of solvent effects on the absorption and emission spectra of the fullerenes.

Excitation energy transfer in covalently linked pheophorbied—porphyrin systems

Steady-state fluorescence, lifetime measurements and time-resolved absorption spectra of the covalently linked hetero dimers consisting of pheophorbide and porphyrin revealed rapid (1011–1012s−1) and efficient singlet—singlet excitation energy transfer from porphyrin unit to pheophorbide.

Direct and sensitized (energy and electron transfer) geometric isomerization of stilbene within zeolites: a comparison between solution and zeolite as reaction media

The trans- and cis-stilbenes upon inclusion in NaY zeolite are thermally stable. Direct excitation and triplet sensitization results in geometric isomerization and the excited state behavior under these conditions are similar to that in solution. Upon direct excitation, a photostationary state consisting of 65% cis and 35% trans isomers is established. Triplet sensitization with 2-acetonaphthone gave a photostationary state consisting of 63% cis and 37% trans isomers. These numbers are similar to the ones obtained in solution. Thus, the presence of cations and the confined space within the zeolite have very little influence on the overall chemistry during direct and triplet sensitization. However, upon electron transfer sensitization with N-methylacridinium (NMA) as the sensitizer within NaY, isomerization from cis-stilbene radical cation to trans-stilbene occurs and the recombination of radical ions results in triplet stilbene. Prolonged irradiation gave a photostationary state (65% cis and 35% trans) similar to triplet sensitization. This behavior is unique to the zeolite and does not take place in solution. Steady state fluorescence measurements showed that the majority of stilbene molecules are close to the N-methylacridinium sensitizer. Diffuse reflectance flash photolysis studies established that independent of the isomer being sensitized only trans radical cation is formed. Triplet stilbene is believed to be generated via recombination of stilbene radical cation and sensitizer radical anion. One should be careful in using acidic HY zeolite as a medium for photoisomerization of stilbenes. In our hands, in these acidic zeolites isomerization dominated the photoisomerization. (C) 2002 Elsevier Science B.V. All rights reserved.

Fluorescence quenching of biologically active carboxamide by aniline and carbon tetrachloride in different solvents using Stern-Volmer plots

Fluorescence quenching of biologically active carboxamide namely (E)-2-(4-chlorobenzylideneamino)-N-(2-chlorophenyl)-4,5,6,7-tetrahydrobe nzo[b]thiophene-3-carboxamide [ECNCTTC] by aniline and carbon tetrachloride (CCl(4)) quenchers in different solvents using steady state method and time resolved method using only one solvent has been carried out at room temperature to understand the role of quenching mechanisms. The Stern-Volmer plot has been found to be linear for all the solvents studied. The probability of quenching per encounter p (p') was determined in all the solvents and was found to be less than unity. Further, from the studies of rate parameters and life time measurements in n-heptane and cyclohexane with aniline and carbon tetrachloride as quenchers have been shown that, the phenomenon of quenching is generally governed by the well-known Stern-Volmer (S-V) plot. The activation energy E(a) (or E(a)') of quenching was determined using the literature values of activation energy of diffusion E(d) and the experimentally determined values of p (or p'). It has been found that, the activation energy E(a) (E(a)') is greater than the activation energy for diffusion E(d) in all solvents. Hence, from the magnitudes of E(a) (or E(a)') as well as p (or p') infer that, the quenching mechanism is not solely due to the material diffusion, but there is also contribution from the activation energy. (C) 2011 Elsevier B.V. All rights reserved.

State space formulation of ammonia reactor dynamics

The specific objective of this paper is to develop a state space model of a tubular ammonia reactor which is the heart of an ammonia plant in a fertiliser complex. A ninth order model with three control inputs and two disturbance inputs is generated from the nonlinear distributed model using linearization and lumping approximations. The lumped model is chosen such that the steady state temperature at the exit of the catalyst bed computed from the simplified state space model is close enough to the one computed from the nonlinear steady state model. The model developed in this paper is very useful for the design of continuous/discrete versions of single variable/multivariable control algorithms.

Spectrally Resolved Resonance Energy Transfer from ZnO:MgO Nanocrystals

Resonance energy transfer (RET) from the visible emission of core−shell ZnO:MgO nanocrystals to Nile Red chromophores, following band gap excitation in the UV, has been investigated for four different nanocrystal sizes. With use of steady state and time-resolved fluorescence spectroscopic measurements the wavelength dependent RET efficiencies have been determined. The RET process in ZnO:MgO nanocrystals occurs from emissions involving trap state recombination. There are two such processes with different RET efficiencies for the same particle size. This is shown to be a consequence of the fact that the recombination processes giving rise to the two emissions are located at different distances from the center of the particle so that the donor−acceptor distances for the two are different, even for the same particle size.

Singlet quenching of tetraphenylporphyrin and its metal derivatives by iron(III) coordination compounds

The quenching of fluorescence of the free-base tetraphenylporphyrin, H2TPP, and its metal derivatives, MgTPP and ZnTPP by diverse iron(III) complexes, [Fe(CN)6]3−, Fe(acac)3, [Fe(mnt)2]−, Fe(Salen)Cl, [Fe4S4(SPh)4]2−·, FeTPPCl and [Fe(Cp)2]+ has been studied both in homogeneous medium (CH3CN) and micellar media, SDS., CTAB and Triton X-100. The quenching efficiencies are analysed in terms of diffusional encounters and it has been possible to separate static quenching components. The quenching constants are dependent on the nature of the ligating atoms around iron(III) and also on the extent of π-conjugation of the ligands. The quenching mechanism has been investigated using steady-state irradiation experiments. Evidence for oxidative quenching by iron(III) complexes was obtained, though the spin multiplicities of the excited electronic states of iron(III) complexes permit both energy and electron transfer mechanisms for quenching of the singlet excited state of the porphyrins.

Inter And Intramolecular Interactions Of Porphyrins With 5,5′-Dithiobis(2-Nitrobenzoic Acid)

meso-Tetraphenylporphyrin and its metal [zinc(II) and copper(II)] derivatives form both inter and intramolecular complexes with 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB). The nature of interaction is predominantly charge transfer (CT) in origin, with the porphyrin functioning as a II-donor and DTNB as an acceptor. Among the covalently linked intramolecular systems, the magnitude of CT interaction varies with the position (of one of the aryl groups of the porphyrin) to which DTNB is attached as ortho meta > para. Steady-state and time-resolved fluorescence studies revealed electron transfer to be the dominant pathway for the fluorescence quenching in these systems. Steady-state photolysis experiments probed using EPR and optical absorption studies have shown that electron transfer (from the excited singlet state of the porphyrin) to DTNB results in the formation of thiyl radical and production of free thiolate anion. It is found that the products of electrochemical reduction of covalently linked porphyrin-DTNB systems are different from those observed for the photochemical studies.

Photophysical and electrochemical redox properties of fixed distance porphyrin-quinone systems

A few fixed distance covalently linked porphyrin-quinone molecules have been synthesized in which a benzoquinone is directly attached to a meso/beta-pyrrole position of tri(phenyl/pentafluorophenyl)/tetraphenylporphyrins. The choice of fluoroarylporphyrins permit modulation of Delta G(ET) values for photoinduced electron-transfer reactions in these systems. All short distance porphyrin-quinone molecules showed efficient quenching of the porphyrin singlet excited state. The electrochemical redox data coupled with the steady-state and time-resolved singlet emission data are analysed to evaluate the dependence of Delta G(ET) values on the rate of electron transfer (k(ET)) in these systems. The meso-trifluoroarylporphyrin-quinones are found to be sensitive probes of the surrounding dielectric environment. Varying solvent polarity on the mechanism of fluorescence quenching and k(ET) values revealed that short donor-acceptor distance and the solvent dielectric relaxation properties play a dominant role. (C) 1999 Elsevier Science S.A. All rights reserved.

Modification of Extended Open Frameworks with Fluorescent Tags for Sensing Explosives: Competition between Size Selectivity and Electron Deficiency

Three new electron-rich metal-organic frameworks (MOF-1-MOF-3) have been synthesized by employing ligands bearing aromatic tags. The key role of the chosen aromatic tags is to enhance the -electron density of the luminescent MOFs. Single-crystal X-ray structures have revealed that these MOFs form three-dimensional porous networks with the aromatic tags projecting inwardly into the pores. These highly luminescent electron-rich MOFs have been successfully utilized for the detection of explosive nitroaromatic compounds (NACs) on the basis of fluorescence quenching. Although all of the prepared MOFs can serve as sensors for NACs, MOF-1 and MOF-2 exhibit superior sensitivity towards 4-nitrotoluene (4-NT) and 2,4-dinitrotoluene (DNT) compared to 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene (TNB). MOF-3, on the other hand, shows an order of sensitivity in accordance with the electron deficiencies of the substrates. To understand such anomalous behavior, we have thoroughly analyzed both the steady-state and time-resolved fluorescence quenching associated with these interactions. Determination of static Stern-Volmer constants (K-S) as well as collisional constants (K-C) has revealed that MOF-1 and MOF-2 have higher K-S values with 4-NT than with TNT, whereas for MOF-3 the reverse order is observed. This apparently anomalous phenomenon was well corroborated by theoretical calculations. Moreover, recyclability and sensitivity studies have revealed that these MOFs can be reused several times and that their sensitivities towards TNT solution are at the parts per billion (ppb) level.

Globally coupled stochastic two-state oscillators: Fluctuations due to finite numbers

Infinite arrays of coupled two-state stochastic oscillators exhibit well-defined steady states. We study the fluctuations that occur when the number N of oscillators in the array is finite. We choose a particular form of global coupling that in the infinite array leads to a pitchfork bifurcation from a monostable to a bistable steady state, the latter with two equally probable stationary states. The control parameter for this bifurcation is the coupling strength. In finite arrays these states become metastable: The fluctuations lead to distributions around the most probable states, with one maximum in the monostable regime and two maxima in the bistable regime. In the latter regime, the fluctuations lead to transitions between the two peak regions of the distribution. Also, we find that the fluctuations break the symmetry in the bimodal regime, that is, one metastable state becomes more probable than the other, increasingly so with increasing array size. To arrive at these results, we start from microscopic dynamical evolution equations from which we derive a Langevin equation that exhibits an interesting multiplicative noise structure. We also present a master equation description of the dynamics. Both of these equations lead to the same Fokker-Planck equation, the master equation via a 1/N expansion and the Langevin equation via standard methods of Ito calculus for multiplicative noise. From the Fokker-Planck equation we obtain an effective potential that reflects the transition from the monomodal to the bimodal distribution as a function of a control parameter. We present a variety of numerical and analytic results that illustrate the strong effects of the fluctuations. We also show that the limits N -> infinity and t -> infinity(t is the time) do not commute. In fact, the two orders of implementation lead to drastically different results.