Pressure-induced charge transfer in lanthanum nickel ferrate (LaNi0.5Fe0.5O3) and analogies to composition-driven charge transfer in dilanthanum cuprate (La2CuO4): an infrared study

A reversible pressure-induced phase transition in lanthanum nickel ferrate (LaNi0.5Fe0.5O3) manifests itself in the infrared spectrum of the transition metal-oxygen stretching (nu(TM-O)) modes by the emergence of new peaks at pressures greater than similar to 1.4 x 10(9) Pa. Analogies to this transition are made by considering charge transfer in dilanthanum cuprate (La2CuO4) and its modification by partial substitution of copper ions by chromium ions.

Generalized model for infrared perception from an engine exhaust

A comprehensive scheme has been developed for the prediction of radiation from engine exhaust and its incidence on an arbitrarily located sensor. Existing codes have been modified for the simulation of flows inside nozzles and jets. A novel view factor computation scheme has been applied for the determination of the radiosities of the discrete panels of a diffuse and gray nozzle surface. The narrowband model has been used to model the radiation from the gas inside the nozzle and the nonhomogeneous jet. The gas radiation from the nozzle inclusive of nozzle surface radiosities have been used as boundary conditions on the jet radiation. Geometric modeling techniques have been developed to identify and isolate nozzle surface panels and gas columns of the nozzle and jet to determine the radiation signals incident on the sensor. The scheme has been validated for intensity and heat flux predictions, and some useful results of practical importance have been generated to establish its viability for infrared signature analysis of jets.

Infrared spectroscopic study of LiCoO2 thin films

Site disorder of Co3+ ions in sputtered films of lithium cobaltite has been examined using infrared spectroscopy. Both transmission and reflectance modes have been used to characterize the nature of IR absorption. It is found that Co3+ in the sputtered films occupy two types of octahedral sites that differ in the nature of second-neighbor environment. Li+ ions exhibit two bands, which may arise from tetrahedral and octahedral site occupancies or from the presence of disordered regions in the films. (C) 2002 Elsevier Science (USA).

Simulation of the infrared spectra of thioacetamide by the extended molecular mechanics method

The infrared spectrum of the matrix-isolated species of thioacetamide has been simulated using the extended molecular mechanics method. The equilibrium structure, vibrational frequencies, dipole moment and infrared absorption intensities of thioacetamide have been calculated in good agreement with the experiment. The vibrational frequencies and infrared absorption intensities for the isotopic molecules (CH2CSNH2)-C-13, (CH3CSNH2)-N-15 and (CH2CSND2)-C-13 have also been calculated consistent with the experiment. The infrared spectra of the matrix isolated species of N- and C- deuterated isotopomers of thioacetamide, CH3CSND2 and CD3CSNH2 have also been simulated in satisfactory agreement with the experimental spectra.

Temperature dependence of infrared and Raman modes in polymeric RbC60

Temperature dependence of the intra-molecular vibrational modes Of C-60 in the quasi-1D polymeric RbC60, across the low temperature transition at similar to50 K, has been probed through infrared (IR) and Raman spectroscopies. With the lowering of temperature, the split IR modes of RbC60 are seen to harden but below 50 K a small but definitive signature of an anomalous softening is observed. In addition, the background IR transmission shows an increase below 50 K with the opening of a well defined gap in the electronic spectrum. The implications of these results, along with those of Raman measurements, are discussed in terms of the interaction of intra-molecular phonons with electrons and spin excitations in the system. (C) 2002 Published by Elsevier Science Ltd.

An infrared spectroscopic study of the low-spin to intermediate-spin state (1A1–3T1) transition in rare earth cobaltates, LnCoO3 (Ln=La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO3 (Ln=La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoO3 and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition.

An infrared spectroscopic study of the low-spin to intermediate-spin state ((1)A(1)-T-3(1)) transition in rare earth cobaltates, LnCoO(3) (Ln = La, Pr and Nd)

Low-spin (LS) to intermediate-spin (IS) state transitions in crystals of LnCoO(3) (Ln = La, Pr and Nd) have been investigated by variable temperature infrared spectroscopy. The spectra reveal the occurrence of the transition around 120, 220 and 275 K, respectively, in LaCoO3,PrCoo(3) and NdCoO3, at which temperatures the intensities of the stretching and the bending modes associated with the LS state decrease, accompanied by an increase in the intensities of the bands due to IS state. The characteristic frequencies of both the spin states decrease with increase in temperature, showing anomalies around the transition. (C) 2001 Published by Elsevier Science B.V.

Simulation of the infrared spectra of N-methylformamide and N-methylacetamide by the extended molecular mechanics method

The infrared spectra of the matrix isolated species of N-methylformamide (NMF) and N-methylacetamide (NMA) and their N-deuterated molecules have been simulated by the extended molecular mechanics method using an empirical force field which includes charges and charge fluxes as coulombic potential parameters. The structural parameters and dipole. moments of NMF and NMA have. also been computed in satisfactory agreement with the experiment. Good agreement between experimental and calculated vibrational frequencies and infrared absorption band intensities for NMF and NMA and their deuterated molecules has been obtained. The vibrational assignments of NMF and NMA are-discussed taking also into account the infrared absorption intensities.

Infrared studies of the phase transitions of alkylammonium halides, RNH3X, and bis-(alkylammonium) tetrahalogenometallates(II), (RNH3)2MX4, (R = alkyl, M = metal, X = Cl or Br)

Internal vibration modes of bis-(alkylammonium) tetrachlorometallates(II) and the corresponding alkylammonium chlorides have been studied through their phase transitions using infrared spectroscopy. The studies show that the vibrational states of alkylammonium ions change markedly through the phase transitions. Spectra of the analogous tetrabromometallates and alkylammonium bromides also confirm this behaviour. There is appreciable motion of the alkylammonium ions in the high-temperature phases; thus, CH3NH+3 ions are essentially undistorted in these phases. The low-temperature, ordered phases show evidence of stronger hydrogen bonding of the cations and for the presence of C—N torsional modes.

Direct Infrared Absorption Spectroscopy of Benzene Dimer

The direct infrared (IR) absorption spectrum of benzene dimer formed in a free-jet expansion was recorded in the 3.3 mu m region for the first time. This has led to the observation of the C H stretching fundamental mode nu(13) (B(1u)), which is both IR and Raman forbidden in the monomer. Moreover, the IR forbidden and Raman allowed nu(7) (E(2g)) mode has been observed as well. These two modes were found to be red-shifted along with the IR allowed nu(20) (E(1u)) mode, as previously reported by Erlekam et al. [Erlekam; Frankowski; Meijer; Gert von Helden J. Chem. Phys. 2006, 124, 171101], using ion-dip spectroscopy, contrary to the blue-shift predicted earlier by theoretical studies. The observation of the nu(13) band indicates that the symmetry is reduced in the dimer, confirming the T-shaped structure observed by Erlekam et al. Our experimental results have not provided any direct evidence for the presence of the parallel displaced geometry, the main objective of the present work, as predicted by theoretical calculations.

Hydrothermal synthesis of CdTe QDs: Their luminescence quenching in the presence of bio-molecules and observation of bistable memory effect in CdTe QD/PEDOT:PSS heterostructure

We report one-pot hydrothermal synthesis of nearly mono-disperse 3-mercaptopropionic acid capped water-soluble cadmium telluride (CdTe) quantum dots (QDs) using an air stable Te source. The optical and electrical characteristics were also studied here. It was shown that the hydrothermal synthesis could be tuned to synthesize nano structures of uniform size close to nanometers. The emissions of the CdTe QDs thus synthesized were in the range of 500-700 nm by varying the duration of synthesis. The full width at half maximum (FWHM) of the emission peaks is relatively narrow (40-90 nm), which indicates a nearly uniform distribution of QD size. The structural and optical properties of the QDs were characterized by transmission electron microscopy (TEM), photoluminescence (PL) and Ultraviolet-visible (UV-Vis) spectroscopy. The photoluminescence quenching of CdTe QDs in the presence of L-cysteine and DNA confirms its biocompatibility and its utility for biosensing applications. The room temperature current-voltage characteristics of QD film on ITO coated glass substrate show an electrically induced switching between states with high and low conductivities. The phenomenon is explained on the basis of charge confinement in quantum dots. (C) 2011 Elsevier B.V. All rights reserved.

Multiphoton absorption in CsLiB6O10 with femtosecond infrared laser pulses

Nonlinear absorption and refraction characteristics of cesium lithium borate (CsLiB6O10) crystal have been studied using Z-scan technique. Ti:sapphire laser with 110 fs pulse width operating at 800 nm wavelength and pulse repetition rate of 1 kHz is used as the source of photons. Intensity of the laser pulse is varied from 0.541 to 1.283 T W/cm2 to estimate the intensity dependence of multiphoton absorption coefficients. Using the theory of multiphoton absorption proposed by Sutherland [ Handbook of Nonlinear Optics, in 2nd ed., edited by D. G. McLean and S. Kirkpatrick, Dekker, New York (2003) ], found that open aperture Z-scan data fit well for the five-photon absorption (5PA) process. 5PA coefficients are obtained by fitting the expressions into the open aperture experimental data for various peak intensities (I00). The nonlinear refractive index n2 estimated from closed aperture Z-scan experiment is 1.075×10−4 cm2/T W at an input peak intensity of 0.723 T W/cm2. The above experiment when repeated with a 532 nm, 6 ns pulsed laser led to an irreversible damage of the sample resulting in an asymmetric open aperture Z-scan profile. This indicates that it is not possible to observe multiphoton absorption in this regime of pulse width using 532 nm laser.

Combined Raman and infrared investigation of the insulator-to-metal transition in NiS(2-x)Se(x) compounds

Ambient-condition Raman spectra were collected in the strongly correlated NiS(1-x)Se(x) pyrite (0 <= x <= 1.2). Two samples (x = 0 and x = 0.55) were studied as a function of pressure up to 10 GPa, and for the x = 0.55 sample the pressure dependence of the infrared reflectivity was also measured (0-10 GPa). This gave a complete picture of the optical response of that system on approaching the metallic state both by application of pressure and/or by Se alloying, which corresponds to a volume expansion. A peculiar nonmonotonic (V-shaped) volume dependence was found for the quasiparticle spectral weight of both pure and Se-doped compounds. In the x = 0.55 sample the vibrational frequencies of the chalcogen dimer show an anomalous volume dependence on entering the metallic phase. The abrupt softening observed, particularly significant for the Se-Se pair, indicates the relevant role of the softness of the Se-Se bond as previously suggested by theoretical calculations.