998 research outputs found
Two-Dimensional Electronic Spectroscopy of Chlorophyll a: Solvent Dependent Spectral Evolution
The interaction of the monomeric chlorophyll Q-band electronic transition with solvents of differing physical-chemical properties is investigated through two-dimensional electronic spectroscopy (2DES). Chlorophyll constitutes the key chromophore molecule in light harvesting complexes. It is well-known that the surrounding protein in the light harvesting complex fine-tunes chlorophyll electronic transitions to optimize energy transfer. Therefore, an understanding of the influence of the environment on the monomeric chlorophyll electronic transitions is important. The Q-band 2DES is inhomogeneous at early times, particularly in hydrogen bonding polar solvents, but also in nonpolar solvents like cyclohexane. Interestingly this inhomogeneity persists for long times, even up to the nanosecond time scale in some solvents. The reshaping of the 2DES occurs over multiple time scales and was assigned mainly to spectral diffusion. At early times the reshaping is Gaussian-like, hinting at a strong solvent reorganization effect. The temporal evolution of the 2DES response was analyzed in terms of a Brownian oscillator model. The spectral densities underpinning the Brownian oscillator fitting were recovered for the different solvents. The absorption spectra and Stokes shift were also properly described by this model. The extent and nature of inhomogeneous broadening was a strong function of solvent, being larger in H-bonding and viscous media and smaller in nonpolar solvents. The fastest spectral reshaping components were assigned to solvent dynamics, modified by interactions with the solute
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We-T classification of diesel fuel droplet impact regimes
A combined experimental and computational investigation of micrometric diesel droplets impacting on a heated aluminium substrate is presented. Dual view high-speed imaging has been employed to visualize the evolution of the impact process at various conditions. The parameters investigated include wall-surface temperature ranging from 140 to 400°C, impact Weber and Reynolds numbers of 19–490 and 141–827, respectively, and ambient pressure of 1 and 2 bar. Six possible post-impact regimes were identified, termed as Stick, Splash, Partial-Rebound, Rebound, Breakup-Rebound and Breakup-Stick, and plotted on the We-T map. Additionally, the temporal variation of the apparent dynamic contact angle and spreading factor have been determined as a function of the impact Weber number and surface temperature. Numerical simulations have also been performed using a two-phase flow model with interface capturing, phase-change and variable physical properties. Increased surface temperature resulted to increased maximum spreading diameter and induced quicker and stronger recoiling behaviour, mostly attributed to the change of liquid viscosity
On the global well-posedness for the Boussinesq system with horizontal dissipation
In this paper, we investigate the Cauchy problem for the tridimensional
Boussinesq equations with horizontal dissipation. Under the assumption that the
initial data is an axisymmetric without swirl, we prove the global
well-posedness for this system. In the absence of vertical dissipation, there
is no smoothing effect on the vertical derivatives. To make up this
shortcoming, we first establish a magic relationship between
and by taking full advantage of the structure of the
axisymmetric fluid without swirl and some tricks in harmonic analysis. This
together with the structure of the coupling of \eqref{eq1.1} entails the
desired regularity.Comment: 32page
Charge carrier induced barrier height reduction at organic heterojunctions
In order to provide an accurate theoretical description of current density
voltage (J-V) characteristics of an organic heterojunction device over a wide
range of electric fields at various temperatures, it is proposed that an
accumulation of charge carriers at the heterojunction will lead to a reduction
in the barrier height across the heterojunction. Two well-known hole
transporting materials, 4,4,4-Tris(N-3-methylphenyl-N-phenyl-amino)
triphenylamine (MTDATA) and
N,N-diphenyl-N,N-bis(1-naphthyl)(1,1-biphenyl)-4,4diamine (NPB) were used to
fabricate unipolar heterojunction devices. It is found that the J-V
characteristics depends strongly on applied bias. The simulated J-V
characteristics of the heterojunction device, with the modified injection
model, are found to be in excellent agreement with the experimental data.Comment: 4 pages, 4 figures, published in Phys. Rev. B Vol. 78, No. 8,
http://link.aps.org/abstract/PRB/v78/e08130
A model for selection of eyespots on butterfly wings
The development of eyespots on the wing surface of butterflies of the family Nympalidae is one of the most studied examples of biological pattern formation.However, little is known about the mechanism that determines the number and precise locations of eyespots on the wing. Eyespots develop around signaling centers, called foci, that are located equidistant from wing veins along the midline of a wing cell (an area bounded by veins). A fundamental question that remains unsolved is, why a certain wing cell develops an eyespot, while other wing cells do not. We illustrate that the key to understanding focus point selection may be in the venation system of the wing disc. Our main hypothesis is that changes in morphogen concentration along the proximal boundary veins of wing cells govern focus point selection. Based on previous studies, we focus on a spatially two-dimensional reaction-diffusion system model posed in the interior of each wing cell that describes the formation of focus points. Using finite element based numerical simulations, we demonstrate that variation in the proximal boundary condition is sufficient to robustly select whether an eyespot focus point forms in otherwise identical wing cells. We also illustrate that this behavior is robust to small perturbations in the parameters and geometry and moderate levels of noise. Hence, we suggest that an anterior-posterior pattern of morphogen concentration along the proximal vein may be the main determinant of the distribution of focus points on the wing surface. In order to complete our model, we propose a two stage reaction-diffusion system model, in which an one-dimensional surface reaction-diffusion system, posed on the proximal vein, generates the morphogen concentrations that act as non-homogeneous Dirichlet (i.e., fixed) boundary conditions for the two-dimensional reaction-diffusion model posed in the wing cells. The two-stage model appears capable of generating focus point distributions observed in nature.
We therefore conclude that changes in the proximal boundary conditions are sufficient to explain the empirically observed distribution of eyespot focus points on the entire wing surface. The model predicts, subject to experimental verification, that the source strength of the activator at the proximal boundary should be lower in wing cells in which focus points form than in those that lack focus points. The model suggests that the number and locations of eyespot foci on the wing disc could be largely controlled by two kinds of gradients along two different directions, that is, the first one is the gradient in spatially varying parameters such as the reaction rate along the anterior-posterior direction on the proximal boundary of the wing cells, and the second one is the gradient in source values of the activator along the veins in the proximal-distal direction of the wing cell
Water Dynamics at Protein Interfaces: Ultrafast Optical Kerr Effect Study
The behavior of water molecules surrounding a protein can have an important bearing on its structure and function. Consequently, a great deal of attention has been focused on changes in the relaxation dynamics of water when it is located at the protein surface. Here we use the ultrafast optical Kerr effect to study the H-bond structure and dynamics of aqueous solutions of proteins. Measurements are made for three proteins as a function of concentration. We find that the water dynamics in the first solvation layer of the proteins are slowed by up to a factor of 8 in comparison to those in bulk water. The most marked slowdown was observed for the most hydrophilic protein studied, bovine serum albumin, whereas the most hydrophobic protein, trypsin, had a slightly smaller effect. The terahertz Raman spectra of these protein solutions resemble those of pure water up to 5 wt % of protein, above which a new feature appears at 80 cm–1, which is assigned to a bending of the protein amide chain
COMPARISON OF SOLUTION ALGORITHM FOR FLOW AROUND A SQUARE CYLINDER
ABSTRACT Numerical accuracy, numerical stability and calculation time are all important factors in the computational fluid dynamics. In this study, we compare two solution algorithms, the Simplified Marker and Cell (SMAC) method in the MAC-type methods and the Semi-Implicit Method for Pressure-Linked Equation (SIMPLE) algorithm in the SIMPLE-type algorithms, with respect to flow around a square cylinder in constant density and unsteady-state calculations using a staggered grid to investigate the numerical accuracy, the numerical stability and the computational time. For the flow around a square cylinder, the SMAC and SIMPLE solutions are in excellent agreement at the Strouhal number, drag and lift coefficients. However, SMAC is more unstable than SIMLE with a large Courant number. The computational time of the SMAC is shorter than that of the SIMPLE with a small Courant number
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Ultrafast Structural Rearrangements in the MLCT Excited State for Copper(I) bis-Phenanthrolines in Solution
Ultrafast excited state structural dynamics of [Cu{sup I}(dmp){sub 2}]{sup +} (dmp = 2,9-dimethyl-1,10-phenanthroline) have been studied to identify structural origins of transient spectroscopic changes during the photoinduced metal-to-ligand-charge-transfer (MLCT) transition that induces an electronic configuration change from Cu(I) (3d{sup 10}) to Cu(II) (3d{sup 9}). This study has important connections with the flattening of the Franck-Condon state tetrahedral geometry and the ligation of Cu(II)* with the solvent observed in the thermally equilibrated MLCT state by our previous laser-initiated time-resolved x-ray absorption spectroscopy (LITR-XAS) results. To better understand the structural photodynamics of Cu(I) complexes, we have studied both [Cu{sup I}(dmp){sub 2}]{sup +} and [Cu{sup I}(dpp){sub 2}]{sup +} (dpp = 2,9-diphenyl-1,10-phenanthroline) in solvents with different dielectric constants, viscosities and thermal diffusivities by transient absorption spectroscopy. The observed spectral dynamics suggest that a solvent-independent inner-sphere relaxation process is occurring despite the large amplitude motions due to the flattening of the tetrahedral coordinated geometry. The singlet fluorescence dynamics of photoexcited [Cu{sup I}(dmp){sub 2}]{sup +} were measured in the coordinating solvent acetonitrile, using the fluorescence upconversion method at different emission wavelengths. At the bluest emission wavelengths, a prompt fluorescence lifetime of 66 fs is attributed to the excited state deactivation processes due to the internal conversion and intersystem crossing at the Franck-Condon state geometry. The differentiation between the prompt fluorescence lifetime with the tetrahedral Franck-Condon geometry and that with the flattened tetrahedral geometry uncovers an unexpected ultrafast flattening process in the MLCT state of [Cu{sup I}(dmp){sub 2}]{sup +}. These results provide guidance for future x-ray structural studies on ultrafast time scale, as well as for synthesis towards its applications in solar energy conversion
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