Nonlinear spectra of ZnO: reverse saturable, two- and three-photon absorption

We present a broadband (460-980 nm) analysis of the nonlinear absorption processes in bulk ZnO, a large-bandgap material with potential blue-to-UV photonic device applications. Using an optical parametric amplifier we generated tunable 1-kHz repetition rate laser pulses and employed the Z-scan technique to investigate the nonlinear absorption spectrum of ZnO. For excitation wavelengths below 500 nm, we observed reverse saturable absorption due to one-photon excitation of the sample, agreeing with rate-equation modeling. Two-and three-photon absorption were observed from 540 to 980 nm. We also determined the spectral regions exhibiting mixture of nonlinear absorption mechanisms, which were confirmed by photoluminescence measurements. (C) 2010 Optical Society of America

Alpha element abundances and gradients in the Milky Way bulge from FLAMES-GIRAFFE spectra of 650 K giants

Aims. We present the analysis of the [alpha/Fe] abundance ratios for a large number of stars at several locations in the Milky Way bulge with the aim of constraining its formation scenario. Methods. We obtained FLAMES-GIRAFFE spectra (R = 22 500) at the ESO Very Large Telescope for 650 bulge red giant branch (RGB) stars and performed spectral synthesis to measure Mg, Ca, Ti, and Si abundances. This sample is composed of 474 giant stars observed in 3 fields along the minor axis of the Galactic bulge and at latitudes b = -4 degrees, b = -6 degrees, b = -12 degrees. Another 176 stars belong to a field containing the globular cluster NGC 6553, located at b = -3 degrees and 5 degrees away from the other three fields along the major axis. Stellar parameters and metallicities for these stars were presented in Zoccali et al. (2008, A&A, 486, 177). We have also re-derived stellar parameters and abundances for the sample of thick and thin disk red giants analyzed in Alves-Brito et al. (2010, A&A, 513, A35). Therefore using a homogeneous abundance database for the bulge, thick and thin disk, we have performed a differential analysis minimizing systematic errors, to compare the formation scenarios of these Galactic components. Results. Our results confirm, with large number statistics, the chemical similarity between the Galactic bulge and thick disk, which are both enhanced in alpha elements when compared to the thin disk. In the same context, we analyze [alpha/Fe] vs. [Fe/H] trends across different bulge regions. The most metal rich stars, showing low [alpha/Fe] ratios at b = -4 degrees disappear at higher Galactic latitudes in agreement with the observed metallicity gradient in the bulge. Metal-poor stars ([Fe/H] < -0.2) show a remarkable homogeneity at different bulge locations. Conclusions. We have obtained further constrains for the formation scenario of the Galactic bulge. A metal-poor component chemically indistinguishable from the thick disk hints for a fast and early formation for both the bulge and the thick disk. Such a component shows no variation, neither in abundances nor kinematics, among different bulge regions. A metal-rich component showing low [alpha/Fe] similar to those of the thin disk disappears at larger latitudes. This allows us to trace a component formed through fast early mergers (classical bulge) and a disk/bar component formed on a more extended timescale.

Dynamic polarizability, Cauchy moments, and the optical absorption spectrum of liquid water: A sequential molecular dynamics/quantum mechanical approach

The dynamic polarizability and optical absorption spectrum of liquid water in the 6-15 eV energy range are investigated by a sequential molecular dynamics (MD)/quantum mechanical approach. The MD simulations are based on a polarizable model for liquid water. Calculation of electronic properties relies on time-dependent density functional and equation-of-motion coupled-cluster theories. Results for the dynamic polarizability, Cauchy moments, S(-2), S(-4), S(-6), and dielectric properties of liquid water are reported. The theoretical predictions for the optical absorption spectrum of liquid water are in good agreement with experimental information.

Electromagnetic absorption cross section of Reissner-Nordstrom black holes

The absorption cross section of Reissner-Nordstrom black holes for the electromagnetic field is computed numerically for arbitrary frequencies. The numerical results are in excellent agreement with the low- and high-frequency limits, which are obtained with analytical methods. Special emphasis is given to the extreme Reissner-Nordstrom black hole case.

Third-order nonlinear spectra and optical limiting of lead oxifluoroborate glasses

We have determined two-photon absorption and nonlinear refraction spectra of the 50BO(1.5) - (50-x)PbF(2) - xPbO glasses (with x = 25, 35, 50 cationic %) at the range of the 470 and 1550 nm. The replacement of fluor atoms by oxygen leads to an increase in the third-order susceptibility, due to the formation of non-bridging oxygens (NBO). The nonlinear index of refraction is one order of magnitude higher than the one for fused silica, and it increases almost twice for the sample with x = 50. This sample has also shown promising features for all-optical switching as well as for optical limiting. (C) 2011 Optical Society of America

Nonlinear refraction and absorption through phase transition in a Nd:SBN laser crystal

Time-resolved Z-scan measurements were performed in a Nd(3+)-doped Sr(0.61)Ba(0.39)Nb(2)O(6) laser crystal through ferroelectric phase transition. Both the differences in electronic polarizability (Delta alpha(p)) and cross section (Delta sigma) of the neodymium ions have been found to be strongly modified in the surroundings of the transition temperature. This observed unusual behavior is concluded to be caused by the remarkable influence that the structural changes associated to the ferro-to-paraelectric phase transition has on the 4f -> 5d transition probabilities. The maximum polarizability change value Delta alpha(p)=1.2x10(-25) cm(3) obtained at room temperature is the largest ever measured for a Nd(3+)-doped transparent material.

Structure, stability, depolarized light scattering, and vibrational spectra of fullerenols from all-electron density-functional-theory calculations

We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C(60)(OH)(n)] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke's three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C(60)(OH)(36). Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1, 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C(60)(OH)(24) isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4, 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.

Solvent Effects in Optical Spectra of ortho-Aminobenzoic Acid Derivatives

We investigated three amino derivatives of ortho-aminobenzoic or anthranilic acid (o-Abz): a) 2-Amino-benzamide (AbzNH(2)); b) 2-Amino-N-methyl-benzamide (AbzNHCH(3)) and c) 2-Amino-N-N`-dimethyl-bezamide (AbzNH(CH(3))(2)), see Scheme 1. We describe the results of ab-initio calculations on the structural characteristics of the compounds and experimental studies about solvent effects in their absorption and steady-state and time-resolved emission properties. Ab-initio calculations showed higher stability for the rotameric conformation in which the oxygen of carbonyl is near to the nitrogen of ortho-amino group. The derivatives present decrease in the delocalization of pi electron, and absorption bands are blue shifted compared to the parent compound absorption, the extent of the effect increasing from to Abz-NH(2) to Abz-NHCH(3) Abz-NH(CH(3))(2). Measurements performed in several solvents have shown that the the dependence of Stokes shift of the derivatives with the orientational polarizability follows the Onsager-Lippert model for general effects of solvent. However deviation occurred in solvents with properties of Bronsted acids, or electron acceptor characteristics, so that hydrogen bonds formed with protic solvents predominates over intramolecular hydrogen bond. In most solvents the fluorescence decay of AbzNH(2) and AbzNHCH(3) was fitted to a single exponential with lifetimes around 7.0 ns and no correlation with polarity of the solvent was observed. The fluorescence decay of AbzN(CH(3))(2) showed lifetimes around 2.0 ns, consistent with low quantum yield of the compound. The spectroscopic properties of the monoamino derivative AbzNHCH(3) are representative of the properties presented by Abz labelled peptides and fatty acids previously studied.

THE COMPTON-THICK SEYFERT 2 NUCLEUS OF NGC 3281: TORUS CONSTRAINTS FROM THE 9.7 mu m SILICATE ABSORPTION

We present mid-infrared (mid-IR) spectra of the Compton-thick Seyfert 2 galaxy NGC 3281, obtained with the Thermal-Region Camera Spectrograph at the Gemini-South telescope. The spectra present a very deep silicate absorption at 9.7 mu m, and [S IV] 10.5 mu m and [Ne II] 12.7 mu m ionic lines, but no evidence of polycyclic aromatic hydrocarbon emission. We find that the nuclear optical extinction is in the range 24 mag <= A(V) <= 83 mag. A temperature T = 300 K was found for the blackbody dust continuum component of the unresolved 65 pc nucleus and the region at 130 pc SE, while the region at 130 pc NW reveals a colder temperature (200 K). We describe the nuclear spectrum of NGC 3281 using a clumpy torus model that suggests that the nucleus of this galaxy hosts a dusty toroidal structure. According to this model, the ratio between the inner and outer radius of the torus in NGC 3281 is R(0)/R(d) = 20, with 14 clouds in the equatorial radius with optical depth of tau(V) = 40 mag. We would be looking in the direction of the torus equatorial radius (i = 60 degrees), which has outer radius of R(0) similar to 11 pc. The column density is N(H) approximate to 1.2 x 10(24) cm(-2) and the iron K alpha equivalent width (approximate to 0.5-1.2 keV) is used to check the torus geometry. Our findings indicate that the X-ray absorbing column density, which classifies NGC 3281 as a Compton-thick source, may also be responsible for the absorption at 9.7 mu m providing strong evidence that the silicate dust responsible for this absorption can be located in the active galactic nucleus torus.

Nuclear and extended spectra of NGC 1068-I. Hints from near-infrared spectroscopy

We report the first simultaneous zJHK spectroscopy on the archetypical Seyfert 2 galaxy NGC 1068 covering the wavelength region 0.9-2.4 mu m. The slit, aligned in the north-south direction and centred in the optical nucleus, maps a region 300 pc in radius at subarcsec resolution, with a spectral resolving power of 360 km s-1. This configuration allows us to study the physical properties of the nuclear gas including that of the north side of the ionization cone, map the strong excess of continuum emission in the K band and attributed to dust and study the variations, both in flux and profile, in the emission lines. Our results show the following. (1) Mid- to low-ionization emission lines are split into two components, whose relative strengths vary with the position along the slit and seem to be correlated with the jet. (2) The coronal lines are single-peaked and are detected only in the central few hundred of pc from the nucleus. (3) The absorption lines indicate the presence of intermediate age stellar population, which might be a significant contributor to the continuum in the near-IR spectra. (4) Through some simple photoionization models we find photoionization as the main mechanism powering the emitting gas. (5) Calculations using stellar features point to a mass concentration inside the 100-200 pc of about 1010 M(circle dot).

Furan interaction with the Si(001)-(2 x 2) surface: structural, energetics, and vibrational spectra from first-principles

In this work we employ the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory, to investigate the adsorption process of furan on the silicon (001) surface. A direct comparison of different adsorption structures with x-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), high resolution electron energy loss spectroscopy (HREELS), near edge x-ray absorption fine structure (NEXAFS), and high resolution spectroscopy experimental data allows us to identify the [4 + 2] cycloaddition reaction as the most probable adsorbate. In addition, theoretical scanning tunnelling microscopy (STM) images are presented, with a view to contributing to further experimental investigations.

Ultrafast dynamics of bis (n-butylimido) perylene thin films excited by two-photon absorption

We report a pump-probe study of the two-photon induced reflectivity changes in bis (n-butylimido) perylene thin films. To enhance the two-photon excitation we deposited bis (n-butylimido) perylene films on top of gold nanoislands. The observed transient response in the reflectivity spectrum of bis (n-butylimido) perylene is due to a depletion of the molecule`s ground state and excited state absorption.

Controlling the absorption and emission properties of polyparaphenylenevinylene films

In this work we used the conversion process of a precursor polymer into polyparaphenylenevinylene (PPV) at low temperatures in order to control the effective conjugation degree of spin-casted PPV films. The absorption and emission spectra of the films were studied by following a partial substitution of chloride counterions from poly(xylylidene tetrahydrothiophenium chloride) (PTHT), used as a precursor, by sodium acid dodecyl benzenesulfonate (DBS), added as a surfactant salt. Upon controlling the DBS amount and conversion temperature (T-c) of PTHT/DBS to PPV films, the band gap of PPV changed from 409 to 506 nm, and 505 to 532 nm, values obtained from absorbance and emission measurements, respectively. Based on these experimental data, we proposed a physical model which represents the chemical structure of PPV as a distribution of conjugated chain segments (like oligomers) alternated by non-conjugated segments (structural defects and/or from the precursor polymer). (C) 2008 Elsevier B.V. All rights reserved.

Absorption and emission properties of LBL PPV films deposited on ITO electrodes

In this work we studied the properties of absorption and emission line shape of layer-by-layer (LBL) poly(p-phenylene vinylene) (PPV) on indium-tin oxide (ITO) electrode. To minimize the PPV thermal conversion effects during the polymer processing, we used a less aggressive leaving group in the precursor polymer; minimizing electrode degradation. LBL ITO/PPV films showed the same absorption and emission line shape compared with LBL PPV films deposited on non-metallic substrates (glass). With this analysis we indirectly observe the decrease in the ITO degradation. Atomic force microscopy (AFM) technique was used to analyze quantitatively the microscopic morphology of the film surface. Results indicated that the substrate topology is not affected, to a large extent, by the use of dodecylbenzensulfonate (DBS) ion. (C) 2008 Elsevier B.V. All rights reserved.

Studies on the resonance Raman spectra of polyaniline obtained with near-IR excitation

The effects of near-IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANIES) and base (PANI-EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm-1 in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm-` were associated to vC-N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm-1 in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to vC=N modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 run causes the deprotonation of PANI-ES and the formation of cross-linking segments having phenazine and/or oxazine rings. For PANI-EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright (c) 2007 John Wiley & Sons, Ltd.