High-pressure Raman and infrared spectroscopic studies of ZrP2O7

High-pressure Raman and mid-infrared spectroscopic studies were carried out on ZrP2O7 to 23.2 and 13 GPa respectively. In the pressure range 0.7-4.3 GPa the lattice mode at 248 cm(-1) disappears, new modes appear around 380 and 1111 cm(-1) and the strong symmetric stretching mode at 476 cm(-1) softens, possibly indicating a subtle phase transition. Above 8 GPa all the modes broaden, and all of the Raman modes disappear beyond 18 GPa. On decompression from the highest pressure, 23.2, to 0 GPa all of the modes reappear but with larger full width at half maximum. Lattice dynamics of the high temperature phase of ZrP2O7 were studied using first principles method and compared with experimental values. (C) 2009 Elsevier Ltd. All rights reserved.

Isomeric identification of methylated naphthalenes using gas phase infrared spectroscopy

We report gas phase mid-infrared spectra of 1- and 2- methyl naphthalenes at 0.2 cm(-1) resolution. Assignment of observed bands have been made using scaled quantum mechanical (SQM) calculations where the force fields rather the frequencies are scaled to find a close fit between observed and calculated bands. The structure of the molecules has been optimized using B3LYP level of theory in conjunction with standard 6-311G** basis set to obtain the harmonic frequencies. Using the force constants in Cartesian coordinates from the Gaussian output, scaled force field calculations are carried out using a modified version of the UMAT program in the QCPE package. Potential energy distributions of the normal modes obtained from such calculations helped us assign the observed bands and identify the unique features of the spectra of 1- and 2-MNs which are important for their isomeric identification.

Ion Transport in a Polymer-Plastic Solid Soft Matter Electrolyte in the Light of Solvent Dynamics and Ion Association

Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state,compliable mechanical strength (similar to 1 MPa), and wide electrochemical voltage stability (>= 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO4)-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO4-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polyme concentration shows an effective increase in trans conformer concentration along with free Li+ ion concentration. This strongly supports the view that enhancement in LiClO4-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO4-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO4-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance H-1 and Li-7 line width measurements.

Optical conductivity of perovskite manganites

We calculate the optical conductivity sigma(omega) for doped rare-earth manganites based on the recently proposed microscopic ``two fluid'' l-b model. We study the temperature dependence of sigma(omega) for La(0.825)Sr(0.175)MnO(3), which has a metallic ground state. At low temperatures, the calculated sigma(omega) shows a ``two-peak'' structure consisting of a far-infrared coherent Drude peak and a broad mid-infrared ``polaron'' peak, as observed in experiments. Upon heating, the Drude peak rapidly loses spectral weight, and sigma(omega) crosses over to having just a single broad mid-infrared peak. The temperature dependence of the mid-infrared peak and the spectral weight transfer between the two peaks are also in agreement with experimental findings. We also study the doping dependence of sigma(omega) for the same compound. The integrated spectral weight under the Drude peak increases rapidly as the doping level is increased from an underdoped, insulating state (x = 0.1) to a highly doped, metallic state (x = 0.3), again in agreement with trends seen experimentally.

Performance study of high operating temperature HgCdTe mid wave infrared detector through numerical modeling

The design of present generation uncooled Hg1-xCdxTe infrared photon detectors relies on complex heterostructures with a basic unit cell of type (n) under bar (+)/pi/(p) under bar (+). We present an analysis of double barrier (n) under bar (+)/pi/(p) under bar (+) mid wave infrared (x = 0.3) HgCdTe detector for near room temperature operation using numerical computations. The present work proposes an accurate and generalized methodology in terms of the device design, material properties, and operation temperature to study the effects of position dependence of carrier concentration, electrostatic potential, and generation-recombination (g-r) rates on detector performance. Position dependent profiles of electrostatic potential, carrier concentration, and g-r rates were simulated numerically. Performance of detector was studied as function of doping concentration of absorber and contact layers, width of both layers and minority carrier lifetime. Responsivity similar to 0.38 A W-1, noise current similar to 6 x 10(-14) A/Hz(1/2) and D* similar to 3.1 x 10(10)cm Hz(1/2) W-1 at 0.1 V reverse bias have been calculated using optimized values of doping concentration, absorber width and carrier lifetime. The suitability of the method has been illustrated by demonstrating the feasibility of achieving the optimum device performance by carefully selecting the device design and other parameters. (C) 2010 American Institute of Physics. doi:10.1063/1.3463379]

High sensitive Static fiber Bragg grating strain sensing using lasers locked to relative frequency reference

A novel high sensitive fiber Bragg grating (FBG) strain sensing technique using lasers locked to relative frequency reference is proposed and analyzed theoretically. Static strain on FBG independent of temperature can be measured by locking frequency of diode laser to the mid reflection frequency of matched reference FBG, which responds to temperature similar to that of the sensor FBG, but is immune to strain applied to the same. Difference between light intensities reflected from the sensor and reference FBGs (proportional to the difference between respective pass band gains at the diode laser frequency) is not only proportional to the relative strain between the sensor and reference FBGs but also independent of servo residual frequency errors. Usage of relative frequency reference avoids all complexities involved in the usage of absolute frequency reference, hence, making the system simple and economical. Theoretical limit for dynamic and static strain sensitivities considering all major noise contributions are of the order of 25 (p epsilon) / root Hz and 1.2 n epsilon / root Hz respectively.

Infrared Photodetectors Based on Reduced Graphene Oxide and Graphene Nanoribbons

The use of reduced graphene oxide (RGO) and graphene nanoribbons (GNRs) as infrared photodetectors is explored, based on recent results dealing with solar cells, light-emitting devices, photodetectors, and ultrafast lasers. IR detection is demonstrated by both RGO and GNRs (see image) in terms of the time-resolved photocurrent and photoresponse. The responsivity of the detectors and their functioning are presented.

Exploring novel methods to achieve sensitivity limits for high operating temperature infrared detectors

A review of high operating temperature (HOT) infrared (IR) photon detector technology vis-a-vis material requirements, device design and state of the art achieved is presented in this article. The HOT photon detector concept offers the promise of operation at temperatures above 120 K to near room temperature. Advantages are reduction in system size, weight, cost and increase in system reliability. A theoretical study of the thermal generation-recombination (g-r) processes such as Auger and defect related Shockley Read Hall (SRH) recombination responsible for increasing dark current in HgCdTe detectors is presented. Results of theoretical analysis are used to evaluate performance of long wavelength (LW) and mid wavelength (MW) IR detectors at high operating temperatures. (C) 2013 Elsevier B.V. All rights reserved.

Infrared spectroscopic study of the rotation of the NH 4+ ion in ammonium halides

Infrared correlation functions, have been obtained from the analysis of band shapes of the 1400 cm−1 bending mode of NH4Cl, NH4Br and NH4I in both the Pm3m and Fm3m phases. The NH 4 + ion seems to undergo relatively free rotation in the high temperature Fm3m phases of these halides.

Infrared Spectra and Conformation of N-Acetylthiourea

Infrared spectra of N-acetylthiourea (ATU) and its N,N,N′-trideuterated compound have been examined in the range 4000–50 cm−1. A complete vibrational assignment with a normal coordinate treatment based on a Urey-Bradley type intramolecular potential function supplemented with valence force function for the out of plane and torsional modes is proposed and the feature of the thioureido vibrations explained. A molecular orbital study by the CNDO/2 method of ATU and its oxygen analog is undertaken and the results are analyzed for a comparative study of the molecular electronic structure and conformation.

Analytical studies of gain optimization in CO2-N2 gasdynamic lasers employing two-dimensional wedge nozzles

An analytical method has been proposed to optimise the small-signaloptical gain of CO2-N2 gasdynamic lasers (gdl) employing two-dimensional (2D) wedge nozzles. Following our earlier work the equations governing the steady, inviscid, quasi-one-dimensional flow in the wedge nozzle of thegdl are reduced to a universal form so that their solutions depend on a single unifying parameter. These equations are solved numerically to obtain similar solutions for the various flow quantities, which variables are subsequently used to optimize the small-signal-gain. The corresponding optimum values like reservoir pressure and temperature and 2D nozzle area ratio also have been predicted and graphed for a wide range of laser gas compositions, with either H2O or He as the catalyst. A large number of graphs are presented which may be used to obtain the optimum values of small signal gain for a wide range of laser compositions without further computations.

A 1h And 13c Magnetic Resonance And Infrared Spectroscopic Study Of Coordinated 2-Aminocyclopentene-1-Dithiocarboxylic Acid And Its S-Methyl Ester

The ligating properties of 2-aminocyclopentene-1-dithiocarboxylic acid and its S-methyl esters were investigated. Complexes with Zn(II), Cd(II) and Hg(II) halides were synthesized and characterized by infrared and proton and carbon-13 NMR studies. The results are concordant with a bidentate coordination of the -CS2 group to the metal ions

Molecular conformation of N,N -diarylthioureas: An assessment by 1H NMR and infrared spectroscopy

Several N,N -dipyridyl- and N-phenyl-N -pyridyl-thioureas were examined in different solvents at various temperatures by 1H NMR in order to study their conformational properties. The influence of concentration and the methyl substituent in the pyridine ring on the chemical shifts of the NH and pyridine groups was investigated. The observed chemical shifts are analysed in terms of the conformational properties of the molecules. Free energy barriers to the internal rotation about the C N bonds have been determined. Infrared spectra have been measured to supplement the NMR studies. Intramolecular hydrogen bonding played a major role in the preferred conformation of pyridylthioureas. The data further revealed an interesting dynamic exchange phenomenon occurring in symmetric N,N -dipyridylthioureas between two intramolecularly hydrogen bonded conformers.

Calorimetric, infrared and ESR studies of the plastically crystalline state of organic compounds

Enthalpy changes of the crystal-plastic and plastic-liquid transitions are related to the temperature range of stability of the plastic phase. Thermodynamics of the plastic state of binary mixtures have been examined. Infrared correlation times, τc, and activation energies have been measured for a few molecules in the plastic state. Molecular tumbling times, τt, have also been measured employing ESR spectra of a spin-probe. Plots of log τc(τt) 1/T are continuous through the plastic-liquid transition. Activation energies for molecular motion seem to vary in the same direction as the ΔH of the plastic-crystal transition. Infrared correlation times of solute molecules in binary solutions in the plastic and the liquid states show interesting variations with solute concentration.