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.

Microstructure characterization of transition films from amorphous to nanocrocrystalline silicon

Hydrogenated silicon (Si:H) films near the threshold of crystallinity were prepared by very high-frequency plasma-enhanced chemical vapor deposition (VHF-PECVD) using a wide range of hydrogen dilution R-H = [H-2]/[SiH4] values of 2-100. The effects of H dilution R-H on the structural properties of the films were investigated using micro-Raman scattering and Fourier transform infrared (FTIR) absorption spectroscopy. The obtained Raman spectra show that the H dilution leads to improvements in the short-range order and the medium-range order of the amorphous network and then to the morphological transition from amorphous to crystalline states. The onset of this transition locates between R-H = 30 and 40 in our case, and with further increasing R-H from 40 to 100, the nanocrystalline volume fraction increases from similar to23% to 43%, and correspondingly the crystallite size enlarges from similar to2.8 to 4.4 nm. The FTIR spectra exhibit that with R-H increasing, the relative intensities of both the SiH stretching mode component at 2100 cm(-1) and wagging mode component at 620 cm(-1) increase in the same manner. We assert that these variations in IR spectra should be associated with the formation of paracrystalline structures in the low H dilution films and nanocrystalline structures in the high H dilution films. (C) 2003 Elsevier Science B.V. All rights reserved.

Effects of the transition dipole moment function on the dynamics of ozone photodissociation: an exact 3D quantum mechanical study

The effects of the transition dipole moment function (TDMF) on the dynamics Of O-3 photodissociation in the Hartley band have been exploited by means of exact 3D time-dependent wavepacket method using the SW potential energy surface [J. Chem. Phys. 78 (1983) 7191]. The calculations show that the explicit inclusion of the TDMF results in slight uniform reductions for the intensities of recurrence peaks of the autocorrelation function and a slight broadening of the absorption spectrum, in comparison with the result where the TDMF is assumed to be constant. The pattern of recurrence structures of the autocorrelation function is essentially unaffected. (C) 2001 Elsevier Science B.V. All rights reserved.

Transition phenomena in a radio-frequency inductively coupled plasma

Changes of the electron dynamics during the mode transition (E- to H-mode) in a hydrogen radio-frequency (rf) inductively coupled plasma are investigated using space and phase resolved optical emission spectroscopy. The E- mode is characterized through relatively weak optical emission which is strongly modulated on a nanosecond time scale during the rf-cycle, with one pronounced maximum per cycle. The modulation in H-mode, with twice the rf-frequency, is significantly weaker while the emission intensities are about two orders of magnitude higher. In particular the transition between these two modes is studied under variations of rf-power input and gas pressure. Characteristic spatio-temporal structures are observed and can be understood in the frame of a simple model combining both coupling mechanisms in the transition regime.

Decay of Cystalline Order and Equilibration during the Solid-to-Plasma Transition Induced by 20-fs Microfocused 92-eV Free-Electron-Laser Pulses

We have studied a solid-to-plasma transition by irradiating Al foils with the FLASH free electron laser at intensities up to 10(16) W/cm(2). Intense XUV self-emission shows spectral features that are consistent with emission from regions of high density, which go beyond single inner-shell photoionization of solids. Characteristic features of intrashell transitions allowed us to identify Auger heating of the electrons in the conduction band occurring immediately after the absorption of the XUV laser energy as the dominant mechanism. A simple model of a multicharge state inverse Auger effect is proposed to explain the target emission when the conduction band at solid density becomes more atomiclike as energy is transferred from the electrons to the ions. This allows one to determine, independent of plasma simulations, the electron temperature and density just after the decay of crystalline order and to characterize the early time evolution.

Modelling Transition Due to Backward Facing Steps Using the Laminar Kinetic Energy Concept

Boundary layer transition estimation and modelling is essential for the design of many engineering products across many industries. In this paper, the Reynolds-averaged Navier–Stokes are solved in conjunction with three additional transport equations to model and predict boundary layer transition. The transition model (referred to as the kTkT–kLkL–ωω model) is based on the kk–ωω framework with an additional transport equation to incorporate the effects low-frequency flow oscillations in the form of a laminar kinetic energy (kLkL). Firstly, a number of rectifications are made to the original kTkT–kLkL–ωω framework in order to ensure an appropriate response to the free-stream turbulence level and to improve near wall predictions. Additionally, the model is extended to incorporate the capability to model transition due to surface irregularities in the form of backward-facing steps with maximum non-dimensional step sizes of approximately 1.5 times the local displacement thickness of the boundary layer where the irregularity is located (i.e k/δ∗⪅1.5k/δ∗⪅1.5) at upstream turbulence intensities in the range 0.01<Tu(%)<0.80.01<Tu(%)<0.8. A novel function is proposed to incorporate transition sensitivity due to aft-facing steps. This paper details the rationale behind the development of this new function and demonstrates its suitability for transition onset estimation on a flat plate at zero pressure gradient.

XUV Emission from Autoionizing Hole States Induced by Intense XUV-FEL at Intensities up to 10(17) W/cm(2)

Aluminium targets were irradiated with 92 eV radiation from FLASH Free Electron Laser at DESY at intensities up to 10(17)W/cm(2) by focussing the beam on target down to a spot size of similar to 1 mu m by means of a parabolic mirror. High resolution XUV spectroscopy was used to identify aluminium emission from complex hole-states. Simulations carried out with the MARIA code show that the emission characterizes the electron heating in the transition phase solid-atomic. The analysis allows constructing a simple model of electron heating via Auger electrons.

Intensities in the v7, v8 and v9 bands of CH2NH, and the harmonic force field of methyleneimine

A high resolution Fourier transform infrared spectrum of methyleneimine, HN=CH2, has been obtained in the gas phase in the region 700 to 1300 cm−1. The rovibrational line intensities of the three lowest fundamentals ν7 (A′), ν8 (A″), and ν9 (A″) have been simulated including all Coriolis interactions between the three bands, and by fitting the observed spectrum the relative signs and magnitudes of the vibrational transition moments have been determined. All of the available spectroscopic data have been used to determine the harmonic force field of methyleneimine.

Theoretical rovibrational line intensities in the electronic ground state of ozone

First-principles calculations of absolute line intensities and rovibrational energies of ozone (O-16(3)) are reported using potential energy and electric dipole moment functions calculated by the internally contracted MRCI approach. The rovibrational energies and eigenfunctions (up to about 8500 cm(-1) and J = 64) were obtained variationally with an exact Hamiltonian in internal valence coordinates. More than 4.8 x 10(6) electric dipole transition matrix elements were calculated for the absolute rovibrational line intensities. They are compared with the values of the HITRAN database. The purely rotational absolute line intensities in the (000) state and the rovibrational intensities for the (001)-(000) band agree to within about 0.3 to 1% for the (0 10)-(000) band to within about 3 to 4%. Excellent agreement with experiment is also achieved for low-lying overtone and combination bands. Inconsistencies are found for the (100)-(000) band overlapping with the antisymmetric stretching fundamental and also for the (002)-(000) antisymmetric stretching overtone. The generated dipole moment function can be used for predicting the absorption intensities in any of the heavier isotopomers, hot bands or the rates of spontaneous emission.

N3-Dye-Induced Visible Laser Anatase-to-Rutile Phase Transition on Mesoporous TiO(2) Films

Titanium dioxide has been extensively used in photocatalysis and dye-sensitized solar cells, where control of the anatase-to-rutile phase transformation may allow the realization of more efficient devices exploiting the synergic effects at anatase/rutile interfaces. Thus, a systematic study showing the proof of concept of a dye-induced morphological transition and an anatase-to-rutile transition based on visible laser (532 nm) and nano/micro patterning of mesoporous anatase (Degussa P25 TiO(2)) films is described for the first time using a confocal Raman microscope. At low laser intensities, only the bleaching of the adsorbed N3 dye was observed. However, high enough temperatures to promote melting/densification processes and create a deep hole at the focus and an extensive phase transformation in the surrounding material were achieved using Is laser pulses of 25-41 mW/cm(2), in resonance with the MLCT band. The dye was shown to play a key role, being responsible for the absorption and efficient conversion of the laser light into heat. As a matter of fact, the dye is photothermally decomposed to amorphous carbon or to gaseous species (CO(x), NO(x), and H(2)O) under a N(2) or O(2) atmosphere, respectively.

Optical transition probabilities and compositional dependence of Judd-Ofelt parameters of Er3+ ions in fluoroindate glass

Fluoroindate glasses containing 1, 2, 3, and 4 mol% ErF3 were prepared in a dry box under an argon atmosphere. Absorption spectra of these glasses at room temperature were obtained. The Judd-Ofelt parameters Ωλ (λ = 2, 4, 6) for f-f transitions of Er3+ ions as well as transition probabilities, branching ratios, radiative lifetimes, and peak cross-sections for stimulated emission of each band were determined. The concentration effect on the intensities is analyzed. The optical properties of the fluoroindate glasses doped with Er3+ ions are compared with those of other glasses described in the literature. © 1995.

Application of laser-induced plasma spectroscopy to the measurement of transition probabilities of Ca I

We present improved experimental transition probabilities for the optical Ca I 4s4p-4s4d and 4s4p-4p2multiplets. The values were determined with an absolute uncertainty of 10%. Transition probabilities have been determined by the branching ratios from the measurement of relative line intensities emitted by laser-induced plasma (LIP). The line intensities were obtained with the target (leadcalcium) placed in argon atmosphere at 6 Torr, recorded at a 2.5 µs delay from the laser pulse, which provides appropriate measurement conditions, and analysed between 350.0 and 550.0 nm. They are measured when the plasma reaches local thermodynamic equilibrium (LTE). The plasma is characterized by electron temperature (T) of 11400 K and an electron number density (Ne) of 1.1 x 1016 cm-3. The influence self-absorption has been estimated for every line, and plasma homogeneity has been checked. The values obtained were compared with previous experimental values in the literature. The method for measurement of transition probabilities using laser-induced plasma as spectroscopic source has been checked.

Unveiling temporal correlations characteristic of a phase transition in the output intensity of a fiber laser

We use advanced statistical tools of time-series analysis to characterize the dynamical complexity of the transition to optical wave turbulence in a fiber laser. Ordinal analysis and the horizontal visibility graph applied to the experimentally measured laser output intensity reveal the presence of temporal correlations during the transition from the laminar to the turbulent lasing regimes. Both methods unveil coherent structures with well-defined time scales and strong correlations both, in the timing of the laser pulses and in their peak intensities. Our approach is generic and may be used in other complex systems that undergo similar transitions involving the generation of extreme fluctuations.

Investigating optical complexity of the phase transition in the intensity of a fibre laser radiation

Fibre lasers have been shown to manifest a laminar-to-turbulent transition when increasing its pump power. In order to study the dynamical complexity of this transition we use advanced statistical tools of time-series analysis. We apply ordinal analysis and the horizontal visibility graph to the experimentally measured laser output intensity. This reveal the presence of temporal correlations during the transition from the laminar to the turbulent lasing regimes. Both methods allow us to unveil coherent structures with well defined time-scales and strong correlations both, in the timing of the laser pulses and in their peak intensities.