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.

Solution combustion synthesis of gamma(L)-Bi(2)MoO(6) and photocatalytic activity under solar radiation

The facile method of solution combustion was used to synthesize gamma(L)-Bi(2)MoO(6). The material was crystallized in a purely crystalline orthorhombic phase with sizes varying from 300 to 500 nm. Because the band gap was 2.51 eV, the degradation of wide variety of cationic and anionic dyes was investigated under solar radiation. Despite the low surface area (< 1 m(2)/g) of the synthesized material, gamma(L)-Bi(2)MoO(6) showed high photocatalytic activity under solar radiation due to its electronic and morphological properties. (C) 2011 Elsevier Ltd. All rights reserved.

Radiation resistance of PFN and PNM-PT relaxor ferroelectrics

The relaxor ferroelectric compositions Pb(Fe1/2Nb1/2)O-3 (PEN) and [Pb(Mg1/3Nb2/3)O-3](0.8)-[PbTiO3](0.2) (PMN-PT) are studied for their radiation response to the high energy heavy ions (50 MeV Li3+, fluence 1 X 10(13)-1 X 10(14) ions/cm(2)) in terms of their structural, dielectric and piezoelectric properties. There was no change in the crystallinity of both the compositions after irradiation as seen from the XRD. The PEN composition did not show much change in the dielectric constant but the value of T-m decreased by 8degreesC. The PMN-PT composition showed an increase in the dielectric constant with increase in the irradiation fluence from 1 x 10(13) to 1 X 10(14) ions/cm(2) with no change in the value of T-m. The piezoelectric coefficient decreased in both the samples after irradiation. Among the compositions studied, PEN is observed to be more radiation resistant to changes in structural and dielectric properties than PM-PT. (C) 2003 Elsevier Ltd. All rights reserved.

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.

Effective thermal conductivity of a heat generating rod bundle dissipating heat by natural convection and radiation

A numerical study of conjugate natural convection and surface radiation in a horizontal hexagonal sheath housing 19 solid heat generating rods with cladding and argon as the fill gas, is performed. The natural convection in the sheath is driven by the volumetric heat generation in the solid rods. The problem is solved using the FLUENT CFD code. A correlation is obtained to predict the maximum temperature in the rod bundle for different pitch-to-diameter ratios and heat generating rates. The effective thermal conductivity is related to the heat generation rate, maximum temperature and the sheath temperature. Results are presented for the dimensionless maximum temperature, Rayleigh number and the contribution of radiation with changing emissivity, total wattage and the pitch-to-diameter ratio. In the simulation of a larger system that contains a rod bundle, the effective thermal conductivity facilitates simplified modelling of the rod bundle by treating it as a solid of effective thermal conductivity. The parametric studies revealed that the contribution of radiation can be 38-65% of the total heat generation, for the parameter ranges chosen. Data for critical Rayleigh number above which natural convection comes into effect is also presented. (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.

Optical diffraction of second-harmonic signals in the LiBO2-Nb2O5 glasses induced by self-organized LiNbO3 crystallites

The nanocrystallites ( ≈ 3 nm) of LiNbO3, evolved in the (100−x)LiBO2-xNb2O5 (5x20, in molar ratio) glass system exhibited intense second-harmonic signals in transmission mode when exposed to infrared (IR) light at λ = 1064 nm. The second-harmonic waves were found to undergo optical diffraction which was attributed to the presence of self-organized submicrometer-sized LiNbO3 crystallites that were grown within the glass matrix along the parallel damage fringes created by the IR laser radiation. Micro-Raman studies carried out on the laser-irradiated samples confirmed the self-organized crystallites to be LiNbO3.