Frequency-domain stimulated and spontaneous light emission signals at molecular junctions

Using a diagrammatic superoperator formalism we calculate optical signals at molecular junctions where a single molecule is coupled to two metal leads which are held at different chemical potentials. The molecule starts in a nonequilibrium steady state whereby it continuously exchanges electrons with the leads with a constant electron flux. Expressions for frequency domain optical signals measured in response to continuous laser fields are derived by expanding the molecular correlation functions in terms of its many-body states. The nonunitary evolution of molecular states is described by the quantum master equation. (C) 2014 AIP Publishing LLC.

In-cylinder investigations and analysis of a SI gas engine fuelled with H-2 and CO rich syngas fuel: Sensitivity analysis of combustion descriptors for engine diagnostics and control

The sensitivity of combustion phasing and combustion descriptors to ignition timing, load and mixture quality on fuelling a multi-cylinder natural gas engine with bio-derived H-2 and CO rich syngas is addressed. While the descriptors for conventional fuels are well established and are in use for closed loop engine control, presence of H-2 in syngas potentially alters the mixture properties and hence combustion phasing, necessitating the current study. The ability of the descriptors to predict abnormal combustion, hitherto missing in the literature, is also addressed. Results from experiments using multi-cylinder engines and numerical studies using zero dimensional Wiebe function based simulation models are reported. For syngas with 20% H-2 and CO and 2% CH4 (producer gas), an ignition retard of 5 +/- 1 degrees was required compared to natural gas ignition timing to achieve peak load of 72.8 kWe. It is found that, for syngas, whose flammability limits are 0.42-1.93, the optimal engine operation was at an equivalence ratio of 1.12. The same methodology is extended to a two cylinder engine towards addressing the influence of syngas composition, especially H-2 fraction (varying from 13% to 37%), on the combustion phasing. The study confirms the utility of pressure trace derived combustion descriptors, except for the pressure trace first derivative, in describing the MBT operating condition of the engine when fuelled with an alternative fuel. Both experiments and analysis suggest most of the combustion descriptors to be independent of the engine load and mixture quality. A near linear relationship with ignition angle is observed. The general trend(s) of the combustion descriptors for syngas fuelled operation are similar to those of conventional fuels; the differences in sensitivity of the descriptors for syngas fuelled engine operation requires re-calibration of control logic for MBT conditions. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Combustion synthesized tetragonal ZrO2: Eu3+ nanophosphors: Structural and photoluminescence studies

Novel crystalline tetragonal ZrO2: Eu3+ phosphors were prepared by a facile and efficient low temperature solution combustion method at 400 +/- 10 degrees C using oxalyl dihydrazide (ODH) as fuel. The powder X-ray diffraction patterns and Rietveld confinement of as formed ZrO2: Eu3+ (1-11 mol%) confirmed the presence of body centered tetragonal phase. The crystallite size estimated from Scherrer's and W-H plots was found to be in the range of 7-17 nm. These results were in good agreement with transmission electron microscopy studies. The calculated microstrain in most of the planes indicated the presence of tensile stress along various planes of the particles. The observed space group (P4(2)/nmc) revealed the presence of cations in the 2b positions (0.75, 0.25, 0.25) and the anions in the 4d positions (0.25, 0.25, 0.45). The optical band gap energies estimated from Wood and Tauc's relation was found to be in the range 4.3-4.7 eV. Photoluminescence (PL) emission was recorded under 394 and 464 nm excitation shows an intense emission peak at 605 nm along with other emission peaks at 537, 592, 605 and 713 nm. These emission peaks were attributed to the transition of D-5(0) -> F-7(J) (J = 0, 1, 2, 3) of Eu3+ ions. The high ratio of Intensity of (D-5(0) -> F-7(2)) and (D-5(0) -> F-7(1)) infers that Eu3+ occupies sites with a low symmetry and without an inversion center. CIE color coordinates indicated the red regions which could meet the needs of illumination devices. (C) 2014 Elsevier B.V. All rights reserved.

DC-Bias-Superposition Characteristics of Ni0.4Zn0.2Mn0.4Fe2O4 Nanopowders Synthesized by Auto-Combustion

Ni0.4Zn0.2Mn0.4Fe2O4 nanopowders were prepared by auto-combustion method. The as-synthesized powders were characterized using X-ray diffraction (XRD) and thermo-gravimetric-differential thermal analysis (TG-DTA), and the powders were densified at different temperatures 400 degrees C, 500 degrees C, 600 degrees C and 700 degrees C/4 hrs using conventional sintering method. The sintered samples were characterized by XRD and transmission electron microscope (TEM). The bulk densities of the samples were increased with an increase of sintering temperature. The grain sizes of all the samples vary in between 18 nm to 30 nm. The hysteresis loops show high saturation magnetization and low coercivity, indicates that it is a soft material. The incremental permeability (permeability with magnetic field superposition) was influenced by both Delta M and H-c. A sample with higher initial permeability and favoured the attainment of a higher incremental permeability. The Q-factor was mainly determined by the sintered density and microstructure. To summarize, a uniform and dense microstructure with relatively small average grain size is favourable for obtaining better dc-bias-superposition characteristics, including permeability and Q-factor.

REDUCED ORDER MODELLING OF COMBUSTION INSTABILITY IN A BACKWARD FACING STEP COMBUSTOR

This paper develops a fully coupled time domain Reduced Order Modelling (ROM) approach to model unsteady combustion dynamics in a backward facing step combustor The acoustic field equations are projected onto the canonical acoustic eigenmodes of the systems to obtain a coupled system of modal evolution equations. The heat release response of the flame is modelled using the G-equation approach. Vortical velocity fluctuations that arise due to shear layer rollup downstream of the step are modelled using a simplified 1D-advection equation whose phase speed is determined from a linear, local, temporal stability analysis of the shear layer just downstream of the step. The hydrodynamic stability analysis reveals a abrupt change in the value of disturbance phase speed from unity for Re < Re-crit to 0.5 for Re > Re-crit, where Remit for the present geometry was found to be approximate to 10425. The results for self-excited flame response show highly wrinkled flame shapes that are qualitatively similar to those seen in prior experiments of acoustically forced flames. The effect of constructive and destructive interference between the two contributions to flame surface wrinkling results in high amplitude wrinkles for the case when K-c -> 1.

Luminescence enhancement in monoclinic CaAl2O4:Eu2+, Cr3+ nanophosphor by fuel-blend combustion synthesis

Eu2+ ion doped into a suitable host results in an efficient luminophore with engineering relevance; however stabilizing this ion in a host is known to be a challenge. Here we report a novel approach for the synthesis of efficient CaAl2O4 phosphor containing Eu2+ luminophore and Cr3+ activator. CaAl2O4:Eu2+, Cr3+ is prepared by a solution combustion (SCS) method using (i) urea, (ii) oxalyl dihydrazide (ODH) and (iii) fuel-blend (in which overall fuel to oxidizer ratio (F/O) = 1). A Multi-channel thermocouple setup is used to measure the flame temperatures to study the nature of combustion of various fuel mixtures. The variation of adiabatic flame temperature is calculated theoretically for different urea/ODH mixture ratios according to thermodynamic concept and correlated with the observed flame temperatures. Blue emission of the CaAl2O4:Eu2+ phosphor is enhanced similar to 20 times using the fuel-blend approach. Using the observed reaction kinetics, and the known chemistry of smoldering type combustion, a mechanism is proposed for the observed stabilization of Eu2+ ion in the fuel-blend case. This also explains the observed improvement in blue light emission. We show that the right choice of the fuel ratio is essential for enhancing photoluminescence (PL) emission. The PL intensity is highest for ODH lean and urea rich combination (i.e. when the ratio of ODH:urea is 1:5); measured color purity is comparable to commercial blue phosphor, BAM:Eu2+. (C) 2015 Elsevier B.V. All rights reserved.

Response to ``Comment on `Frequency-domain stimulated and spontaneous light emission signals at molecular junctions''' J. Chem. Phys. 142, 137101 (2015)]

In a recent work [U. Harbola, B. K. Agrawalla, and S. Mukamel, J. Chem. Phys. 141, 074107 (2014)], we have presented a superoperator (Liouville space) diagrammatic formulation of spontaneous and stimulated optical signals from current-carrying molecular junctions. We computed the diagrams that contribute to the spontaneous light emission SLE (fluorescence and Raman) signal using a diagrammatic method which clearly distinguishes between the Raman and the fluorescence contributions. We pointed out some discrepancies with the work of Galperin, Ratner and Nitzan (GRN) [M. Galperin, M. A. Ratner and, A. Nitzan, J. Chem. Phys. 130, 144109 (2009)]. In their response [M. Galperin, M. A. Ratner and A. Nitzan, “Comment on‘ Frequency-domain stimulated and spontaneous light emission signals at molecular junctions’” [J. Chem. Phys. 141, 074107 (2014)], J. Chem. Phys. 142, 137101 (2015)] to our work, GRN have argued that there are no differences in the choice of Raman diagrams in both works. Here we reply to their points and show where the differences exist.

Spontaneous Lorentz violation: the case of infrared QED

It is by now clear that the infrared sector of quantum electrodynamics (QED) has an intriguingly complex structure. Based on earlier pioneering work on this subject, two of us recently proposed a simple modification of QED by constructing a generalization of the U(1) charge group of QED to the ``Sky'' group incorporating the well-known spontaneous Lorentz violation due to infrared photons, but still compatible in particular with locality (Balachandran and Vaidya, Eur Phys J Plus 128:118, 2013). It was shown that the ``Sky'' group is generated by the algebra of angle-dependent charges and a study of its superselection sectors has revealed a manifest description of spontaneous breaking of the Lorentz symmetry. We further elaborate this approach here and investigate in some detail the properties of charged particles dressed by the infrared photons. We find that Lorentz violation due to soft photons may be manifestly codified in an angle-dependent fermion mass, modifying therefore the fermion dispersion relations. The fact that the masses of the charged particles are not Lorentz invariant affects their spin content, and time dilation formulas for decays should also get corrections.

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.

Metal-insulator transition characteristics of vanadium dioxide thin films synthesized by ultrasonic nebulized spray pyrolysis of an aqueous combustion mixture

We report the synthesis of high quality vanadium dioxide (VO2) thin films by a novel spray pyrolysis technique, namely ultrasonic nebulized spray pyrolysis of aqueous combustion mixture (UNSPACM). This simple and cost effective two step process involves synthesis of a V2O5 film on an LaAlO3 substrate followed by a controlled reduction to form single phase VO2. The formation of M1 phase (p21/c) is confirmed by Raman spectroscopic studies. A thermally activated metal-insulator transition (MIT) was observed at 61 degrees C, where the resistivity changes by four orders of magnitude. Activation energies for the low conduction phase and the high conduction phase were obtained from temperature variable resistance measurements. The infrared spectra also show a dramatic change in reflectance from 13% to over 90% in the wavelength range of 7-15 mu m. This indicates the suitability of the films for optical switching applications at infrared frequencies.

High photoconductive combustion synthesized TiO2 derived nanobelts for photocatalytic water purification under solar irradiation

Drinking water scarcity is a major issue that needs to be addressed seriously. Water needs to be purified from organic pollutants and bacterial contamination. In this study, sunlight driven photocatalysis for the degradation of dyes and bacterial inactivation has been conducted over TiO2 nanoparticles (CST) and TiO2 nanobelts (CSTNB). TiO2 nanoparticles were synthesized by a solution combustion process using ascorbic acid as a fuel. Acid etched TiO2 nanobelts (CSTNB) were synthesized using combustion synthesized TiO2 as a novel precursor. The mechanism of formation of TiO2 nanobelts was hypothesized. The antibacterial activity of combustion synthesized TiO2 and acid etched TiO2 nanobelts were evaluated against Escherichia coli and compared against commercial TiO2. Various characterization studies like X-ray diffraction analysis, BET surface area analysis, diffused reflectance measurements were performed. Microscopic structures and high resolution images were analyzed using scanning electron microscopy, transmission electron microscopy. The extent of photo-stability and reusability of the catalyst was evaluated by conducting repeated cycles of photo degradation experiments and was compared to the commercial grade TiO2. The reactive radical species responsible for high photocatalytic and antibacterial activity has been determined by performing multiple scavenger reactions. The excellent charge transfer mechanism, high generation of hydroxyl and hole radicals resulted in enhanced photocatalytic activity of the acid etched TiO2 nanobelts compared to commercial TiO2 and nanobelts made from commercial TiO2.

QUANTITATIVE OH PLANAR LASER INDUCED FLUORESCENCE DIAGNOSTICS OF SYNGAS AND METHANE COMBUSTION IN A CAVITY COMBUSTOR

The current work reports quantitative OH species concentration in the cavity of a trapped vortex combustor (TVC) in the context of mixing and flame stabilization studies using both syngas and methane fuels. Planar laser induced fluorescence (PLIF) measurements of OH radical obtained using a Nd: YAG pumped dye laser are quantified using a flat flame McKenna burner. The momentum flux ratio (MFR), defined as the ratio of the cavity fuel jet momentum to that of the guide vane air stream, is observed to be a key governing parameter. At high MFRs similar to 4.5, the flame front is observed to form at the interface of the fuel jet and the air jet stream. This is substantiated by velocity vector field measurements. For syngas, as the MFR is lowered to similar to 0.3, the fuel-air mixing increases and a flame front is formed at the bottom and downstream edge of the cavity where a stratified charge is present. This trend is observed for different velocities at similar equivalence ratios. In case of methane combustion in the cavity, where the MFRs employed are extremely low at similar to 0.01, a different mechanism is observed. A fuel-rich mixture is now observed at the center of the cavity and this mixture undergoes combustion. On further increase of the cavity equivalence ratio, the rich mixture exceeds the flammability limit and forms a thin reaction zone at the interface with air stream. As a consequence, a shear layer flame at the top of the cavity interface with the mainstream is also observed. The equivalence ratio in the cavity also determines the combustion characteristics in the case of fuel-air mixtures that are formed as a result of the mixing. Overall, flame stabilization mechanisms have been proposed, which account for the wide range of MFRs and premixing in the mainstream as well.

Role of Fuel on Cation Disorder in Magnesium Aluminate (MgAl2O4) Spinel Prepared by Combustion Synthesis

Magnesium aluminate spinel (MgAl2O4) forms an interesting system having tetrahedral and octahedral voids filled with near similar sized divalent Mg2+ and trivalent Al3+ cations. Structural disorder (e.g., Mg-Al antisite defects) can be tuned by synthetic conditions. This study reports the evolution of Mg/Al disorder in MgAl2O4 prepared by combustion synthesis using different types of fuels. The effect of nature of fuel and the final calcination temperature (600 degrees C-900 degrees C for 9h) on degree of cation ordering has been investigated combining powder X-ray (XRD) and neutron (NPD) diffraction. The results indicate very high degree of inversion in the samples crystallized at low annealing temperature, which on further annealing reduces toward the thermodynamically stable values. Raman spectroscopy, probing MgO4, and AlO4 tetrahedral bonds, confirmed the results at a local level.

Effect of Sm3+-Gd3+ on structural, electrical and magnetic properties of Mn-Zn ferrites synthesized via combustion route

Nanocrystalline Mn0.4Zn0.6SmxGdyFe2-(x+y)O4 (x = y = 0.01, 0.02, 0.03, 0.04 and 0.05) were synthesized by combustion route. The detailed structural studies were carried out through X-ray diffractometer (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM). The results confirms the formation of mixed spine phase with cubic structure due to the distortion created with co-dopants substitution at Fe site in Mn-Zn ferrite lattice. Further, the crystallite size increases with an increase of Sm3+-Gd3+ ions concentration while lattice parameter and lattice strain decreases. Furthermore, the effect of Sm-Gd co-doping in Mn-Zn ferrite on the room temperature electrical (dielectric studies) studies were carried out in the wide frequency range 1 GHz-5 GHz. The magnetic studies were carried out using vibrating sample magnetometer (VSM) under applied magnetic field of 1.5T and also room temperature electron paramagnetic resonance (EPR) spectra's were recorded. From the results of dielectric studies, it shows that the real and imaginary part of permittivities are increasing with variation of Gd3+ and Sm3+ concentration. The magnetic studies reveal the decrease of remnant, saturation magnetization and coercivity with increasing of Sm3+-Gd3+ ion concentration. The g-value, peak-to-peak line width and spin concentration evaluated from EPR spectra correlated with cations occupancy. The electromagnetic properties clearly indicate that these materials are the good candidates which are useful at L and C band frequency. (C) 2015 Elsevier B.V. All rights reserved.

Study on Low Temperature DC Electrical Conductivity of SnO2 Nanomaterial Synthesized by Simple Gel Combustion Method

Nanocrystalline tin oxide (SnO2) material of different particle size was synthesized using gel combustion method by varying oxidizer (HNO3) and keeping fuel as a constant. The prepared samples were characterized by X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM) and Energy Dispersive Analysis X-ray Spectroscope (EDAX). The effect of oxidizer in the gel combustion method was investigated by inspecting the particle size of nano SnO2 powder. The particle size was found to be increases with the increase of oxidizer from 8 to 12 moles. The X-ray diffraction patterns of the calcined product showed the formation of high purity tetragonal tin (IV) oxide with the particle size in the range of 17 to 31 nm which was calculated by Scherer's formula. The particles and temperature dependence of direct (DC) electrical conductivity of SnO2 nanomaterial was studied using Keithley source meter. The DC electrical conductivity of SnO2 nanomaterial increases with the temperature from 80 to 300K and decrease with the particle size at constant temperature.