Long range resonance energy transfer from a dye molecule to graphene has (distance)-4 dependence

In our previous report on resonance energy transfer from a dye molecule to graphene [J. Chem. Phys.129, 054703 (2008)], we had derived an expression for the rate of energy transfer from a dye to graphene. An integral in the expression for the rate was evaluated approximately. We found a Yuwaka-type dependence of the rate on the distance. We now present an exact evaluation of the integral involved, leading to very interesting results. For short distances (z < 20 A), the present rate and the previous rate are in good agreement. For larger distances, the rate is found to have a z(-4) dependence on the distance, exactly. Thus we predict that for the case of pyrene on graphene, it is possible to observe fluorescence quenching up to a distance of 300 A. This is in sharp contrast to the traditional fluorescence resonance energy transfer where the quenching is observable only up to 100 A.

Excitation energy transfer from dye molecules to doped graphene

Recently, we have reported theoretical studies on the rate of energy transfer from an electronically excited molecule to graphene. It was found that graphene is a very efficient quencher of the electronically excited states and that the rate infinity z(-4). The process was found to be effective up to 30 nm which is well beyond the traditional FRET limit. In this report, we study the transfer of an amount of energy (h) over bar Omega from a dye molecule to doped graphene. We find a crossover of the distance dependence of the rate from z(-4) to exponential as the Fermi level is increasingly shifted into the conduction band, with the crossover occurring at a shift of the Fermi level by an amount (h) over bar Omega/2.

Heterogeneity in Dye-TiO2 Interactions Dictate Charge Transfer Efficiencies for Diketopyrrolopyrrole-Based Polymer Sensitized Solar Cells

Power conversion efficiency of a solar cell is a complex parameter which usually hides the molecular details of the charge generation process. For rationally tailoring the overall device efficiency of the dye-sensitized solar cell, detailed molecular understanding of photoinduced reactions at the dye-TiO2 interface has to be achieved. Recently, near-IR absorbing diketopyrrolopyrrole-based (DPP) low bandgap polymeric dyes with enhanced photostabilities have been used for TiO2 sensitization with moderate efficiencies. To improve the reported device performances, a critical analysis of the polymerTiO(2) interaction and electron transfer dynamics is imperative. Employing a combination of time-resolved optical measurements complemented by low temperature EPR and steady-state Raman spectroscopy on polymerTiO(2) conjugates, we provide direct evidence for photoinduced electron injection from the TDPP-BBT polymer singlet state into TiO2 through the C-O group of the DPP-core. A detailed excited state description of the electron transfer process in films reveals instrument response function (IRF) limited (<110 fs) charge injection from a minor polymer fraction followed by a picosecond recombination. The major fraction of photoexcited polymers, however, does not show injection indicating pronounced ground state heterogeneity induced due to nonspecific polymerTiO(2) interactions. Our work therefore underscores the importance of gathering molecular-level insight into the competitive pathways of ultrafast charge generation along with probing the chemical heterogeneity at the nanoscale within the polymerTiO2 films for optimizing photovoltaic device efficiencies.

Distance dependence of fluorescence resonance energy transfer

Deviations from the usual R (-6) dependence of the rate of fluorescence resonance energy transfer (FRET) on the distance between the donor and the acceptor have been a common scenario in the recent times. In this paper, we present a critical analysis of the distance dependence of FRET, and try to illustrate the non R (-6) type behaviour of the rate for the case of transfer from a localized electronic excitation on the donor, a dye molecule to three different energy acceptors with delocalized electronic excitations namely, graphene,two-dimensional semiconducting sheet and the case of such a semiconducting sheet rolled to obtain a nanotube. We use simple analytic models to understand the distance dependence in each case.

Excitation energy transfer from a fluorophore to single-walled carbon nanotubes

We study the process of electronic excitation energy transfer from a fluorophore to the electronic energy levels of a single-walled carbon nanotube. The matrix element for the energy transfer involves the Coulombic interaction between the transition densities on the donor and the acceptor. In the Foumlrster approach, this is approximated as the interaction between the corresponding transition dipoles. For energy transfer from a dye to a nanotube, one can use the dipole approximation for the dye, but not for the nanotube. We have therefore calculated the rate using an approach that avoids the dipole approximation for the nanotube. We find that for the metallic nanotubes, the rate has an exponential dependence if the energy that is to be transferred, h is less than a threshold and a d(-5) dependence otherwise. The threshold is the minimum energy required for a transition other than the k(i,perpendicular to)=0 and l=0 transition. Our numerical evaluation of the rate of energy transfer from the dye pyrene to a (5,5) carbon nanotube, which is metallic leads to a distance of similar to 165 A degrees up to which energy transfer is appreciable. For the case of transfer to semiconducting carbon nanotubes, apart from the process of transfer to the electronic energy levels within the one electron picture, we also consider the possibility of energy transfer to the lowest possible excitonic state. Transfer to semiconducting carbon nanotubes is possible only if>=epsilon(g)-epsilon(b). The long range behavior of the rate of transfer has been found to have a d(-5) dependence if h >=epsilon(g). But, when the emission energy of the fluorophore is in the range epsilon(g)>h >=epsilon(g)-epsilon(b), the rate has an exponential dependence on the distance. For the case of transfer from pyrene to the semiconducting (6,4) carbon nanotube, energy transfer is found to be appreciable up to a distance of similar to 175 A degrees.

Kinetics and mechanism for dye degradation with ionic Pd-substituted ceria

The degradation of the dye, Orange G, was carried out in the presence of H2O2 and Pd-substituted/impregnated CeO2. The effects of pH, initial dye concentration, initial H2O2 concentration, temperature, catalyst loading, and Pd content in the catalyst on the degradation of the dye were investigated. Eight to twelve percent degradation of the dye was obtained in 1 h when the reaction was carried out in the presence of CeO2 or H2O2 or Pd-substituted/impregnated CeO2 while 17% and 97% degradation was obtained when H2O2 was used with Pd-impregnated CeO2 and Pd-substituted CeO2, respectively. This difference clearly indicated that the ionic substitution of Pd played a key role in the degradation of the dye. A mechanism for the reaction was proposed based upon the catalyst structure and the electron transfer processes that take place in the metal ion substituted system in a reducible oxide. The reaction was found to follow first order kinetics and the influence of all the parameters on the degradation kinetics was compared using the rate constants. (c) 2011 Elsevier B.V. All rights reserved.

Enhanced sunlight photocatalytic activity of Ag3PO4 decorated novel combustion synthesis derived TiO2 nanobelts for dye and bacterial degradation

This study demonstrates the synthesis of TiO2 nanobelts using solution combustion derived TiO2 with enhanced photocatalytic activity for dye degradation and bacterial inactivation. Hydrothermal treatment of combustion synthesized TiO2 resulted in unique partially etched TiO2 nanobelts and Ag3PO4 was decorated using the co-precipitation method. The catalyst particles were characterized using X-ray diffraction analysis, BET surface area analysis, diffuse reflectance and electron microscopy. The photocatalytic properties of the composites of Ag3PO4 with pristine combustion synthesized TiO2 and commercial TiO2 under sunlight were compared. Therefore the studies conducted proved that the novel Ag3PO4/unique combustion synthesis derived TiO2 nanobelt composites exhibited extended light absorption, better charge transfer mechanism and higher generation of hydroxyl and hole radicals. These properties resulted in enhanced photodegradation of dyes and bacteria when compared to the commercial TiO2 nanocomposite. These findings have important implications in designing new photocatalysts for water purification.

EFFECT OF PLUME DYNAMICS FOR HEAT TRANSFER ENHANCEMENT AT SOLID-LIQUID INTERFACE

The present paper analyzes the effects of plumes for heat transfer enhancement at solid-liquid interface taking both smooth and grooved surfaces. The experimental setup consists of a tank of dimensions 265 x 265 x 300 (height) containing water. The bottom surface was heated and free surface of the water was left open to the ambient. In the experiments, the bottom plate had either a smooth surface or a grooved surface. We used 90 V-grooved rough surfaces with two groove heights, 10mm and 3mm. The experiment was done with water layer depths of 90mm and 140mm, corresponding to values of aspect ratio(AR) equal to 2.9 and 1.8 respectively. Thymol blue, a pH sensitive dye, was used to visualize the flow near the heated plate. The measured heat transfer coefficients over the grooved surfaces were higher compared that over the smooth surface. The enhanced heat transport in the rough cavities cannot be ascribed to the increase in the contact area, rather it must be the local dynamics of the thermal boundary layer that changes the heat transport over the rough surface.

A dendrimer facilitates resonance energy transfer between hydrophobic aromatic guest molecules in water

A water soluble third generation poly(alkyl aryl ether) dendrimer was examined for its ability to solubilize hydrophobic polyaromatic molecules in water and facilitate non-radiative resonance energy transfer between them. One to two orders of magnitude higher aqueous solubilities of pyrene (PY), perylene (PE), acridine yellow (AY) and acridine orange (AO) were observed in presence of a defined concentration of the dendrimer. A reduction in the quantum yield of the donor PY* emission and a partial decrease in lifetime of the donor excited state revealed the occurrence of energy transfer from dendrimer solubilized excited PY to ground state PE molecules, both present within a dendrimer. The energy transfer efficiency was estimated to be similar to 61%. A cascade resonance energy transfer in a three component system, PY*-to-PE-to-AY and PY*-to-PE-to-AO, was demonstrated through incorporation of AY or AO in the two component PY-PE system. In the three-component system, excitation of PY resulted in emission from AY or AO via a cascade energy transfer process. Careful choice of dye molecules with good spectral overlap and the employment of dendrimer as the medium enabled us to expand absorption-emission wavelengths, from similar to 330 nm to similar to 600 nm in aqueous solution. (C) 2015 Elsevier B.V. All rights reserved.

Unsteady flow and heat transfer between rotating coaxial disks

A study is made on the flow and heat transfer of a viscous fluid confined between two parallel disks. The disks are allowed to rotate with different time dependent angular velocities, and the upper disk is made to approach the lower one with a constant speed. Numerical solutions of the governing parabolic partial differential equations are obtained through a fourth-order accurate compact finite difference scheme. The normal forces and torques that the fluid exerts on the rotating surfaces are obtained at different nondimensional times for different values of the rate of squeezing and disk angular velocities. The temperature distribution and heat transfer are also investigated in the present analysis.

Effect Of Directionality Of Grinding Marks On Friction And Formation Of Transfer Layer

Surface texture influences friction and transfer layer formation during sliding. In the present investigation, basic studies were conducted using inclined pin-on-plate sliding tester to understand the effect of directionality of surface grinding marks of hard material on friction and transfer layer formation during sliding against soft materials. 080 M40 steel plates were ground to attain different surface roughness with unidirectional grinding marks. Then pins made of soft materials such as pure Al, pure Mg and Al-Mg alloy were slid against the prepared steel plates. Grinding angle (i.e., the angle between direction of sliding and grinding marks) was varied between 0 degrees and 90 degrees in the tests. Experiments were conducted under both dry and lubricated conditions on each plate in ambient environment. It was observed that the transfer layer formation and the coefficient of friction, which has two components adhesion and plowing - depend primarily on the directionality of grinding marks of the harder mating surface, and independent of surface roughness of the harder mating surface. For the case of pure Mg, stick-slip phenomenon was observed under dry condition for all grinding angles and it was absent upto 20 degrees grinding angles under lubricated condition. However, for the case of Al, it was observed only under lubricated conditions for angles exceeding 20 degrees. As regards the alloy, namely, Al-Mg alloy, it, was absent in both conditions. For the case of pure Mg and Al, it was observed that the amplitude of stick-slip motion primarily depends on plowing component of friction. The grinding angle effect on coefficient of friction was attributed to the variation of plowing component of friction with grinding angle.

Studies On Friction And Formation Of Transfer Layer In Hcp Metals

Surface texture plays an important role in the frictional behavior and transfer layer formation of contacting surfaces. In the present investigation, basic experiments were conducted using an inclined pin-on-plate sliding apparatus to better understand the role of surface texture on the coefficient of friction and the formation of a transfer layer. In the experiments, soft HCP materials such as pure Mg and pure Zn were used for the pins and a hardened 080 M40 steel was used for the plate. Two surface parameters of the steel plates—roughness and texture—were varied in tests that were conducted at a sliding speed of 2 mm/s in ambient conditions under both dry and lubricated conditions. The morphologies of the worn surfaces of the pins and the formation of the transfer layer on the counter surfaces were observed using a scanning electron microscope. In the experiments, the occurrence of stick-slip motion, the formation of a transfer layer, and the value of friction were recorded. With respect to the friction, both adhesion and plowing components were analyzed. Based on the experimental results, the effect of surface texture on the friction was attributed to differences in the amount of plowing. Both the plowing component of friction and the amplitude of stick-slip motion were determined to increase surface textures that promote plane strain conditions and decrease the textures that favor plane stress conditions.

Flow and heat transfer in a stagnation-point flow over a stretching sheet with a magnetic field

The flow and heat transfer problem in the boundary layer induced by a continuous moving surface is important in many manufacturing processes in industry such as the boundary layer along material handling conveyers, the aerodynamic extrusion of plastic sheet, the cooling of an infinite metalic plate in a cooling bath (which may also be electrolyte). Glass blowing, continuous casting and spinning of fibres also involve the flow due to a stretching surface. Sakiadis [1] was the first to study the flow induced by a semi-infinite moving wall in an ambient fluid. On the other hand, Crane [2] first studied the flow over a linearly stretching sheet in an ambient fluid. Subsequently, Crane [3] also investigated the corresponding heat transfer problem. Since then several authors [4-8] have studied various aspects of this problem such as the effects of mass transfer, variable wall temperature, constant heat flux, magnetic field etc. Recently, Andersson [9] has obtained an exact solution of the Navier-Stokes equations for the MHD flow over a linearly stretching sheet in an ambient fluid. Also Chiam [10] has studied the heat transfer with variable thermal conductivity on a stretching sheet when the velocities of the sheet and the free stream are equal.

Free Energy Gap Dependence of the Electron-Transfer Rate from the Inverted to the Normal Region

numerical study of the free energy gap (FEG) dependence of the electron-transfer rate in polar solvents is presented. This study is based on the generalized multidimensional hybrid model, which not only includes the solvent polarization and the molecular vibration modes, but also the biphasic polar response of the solvent. The free energy gap dependence is found to be sensitive to several factors, including the solvent relaxation rate, the electronic coupling between the surfaces, the frequency of the high-frequency quantum vibrational mode, and the magnitude of the solvent reorganization energy. It is shown that in some cases solvent relaxation can play an important role even in the Marcus normal regime. The minimal hybrid model involves a large number of parameters, giving rise to a diverse non-Marcus FEG behavior which is often determined collectively by these parameters. The model gives the linear free energy gap dependence of the logarithmic rate over a substantial range of FEG, spanning from the normal to the inverted regime. However, even for favorable values of the relevant parameters, a linear free energy gap dependence of the rate could be obtained only over a range of 5000-6000 cm(-1) (compared to the experimentally observed range of 10000 cm(-1) reported by Benniston et al.). The present work suggests several extensions/generalizations of the hybrid model which might be necessary to fully understand the observed free energy gap dependence.

A combined experimental and theoretical study of the charge-transfer compound between C60Br8 and tetrathiafulvalene

C60Br8, unlike C60Br6 and C60Cl6, forms a solid charge-transfer compound with tetrathiafulvalene (TTF), the composition being C60Br8(TTF)(8). The unique complex-forming property of C60Br8 can be understood on the basis of the electronic structures of the halogenated derivatives of C-60. Molecular orbital calculations show that the low LUMO energy of C60Br8 compared with the other halogen derivatives renders the formation of the complex with TTF favourable, the four virtual LUMOs being able to accept 8 electrons. The Raman spectrum of C60Br8(TTF)(8) shows a marked softening of the bands (-46 cm(-1) on average) with respect to C60Br8 suggesting that indeed 8 electrons are transferred per C60Br8 molecule, one from each TTF molecule. The complex is weakly paramagnetic and shows a magnetic transition around 80 K.