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.

Study of the optical and magnetic properties of pyrimidine in water combining PCM and QM/MM methodologies

The solvent effects on the low-lying absorption spectrum and on the (15)N chemical shielding of pyrimidine in water are calculated using the combined and sequential Monte Carlo simulation and quantum mechanical calculations. Special attention is devoted to the solute polarization. This is included by an iterative procedure previously developed where the solute is electrostatically equilibrated with the solvent. In addition, we verify the simple yet unexplored alternative of combining the polarizable continuum model (PCM) and the hybrid QM/MM method. We use PCM to obtain the average solute polarization and include this in the MM part of the sequential QM/MM methodology, PCM-MM/QM. These procedures are compared and further used in the discrete and the explicit solvent models. The use of the PCM polarization implemented in the MM part seems to generate a very good description of the average solute polarization leading to very good results for the n-pi* excitation energy and the (15)N nuclear chemical shield of pyrimidine in aqueous environment. The best results obtained here using the solute pyrimidine surrounded by 28 explicit water molecules embedded in the electrostatic field of the remaining 472 molecules give the statistically converged values for the low lying n-pi* absorption transition in water of 36 900 +/- 100 (PCM polarization) and 36 950 +/- 100 cm(-1) (iterative polarization), in excellent agreement among one another and with the experimental value observed with a band maximum at 36 900 cm(-1). For the nuclear shielding (15)N the corresponding gas-water chemical shift obtained using the solute pyrimidine surrounded by 9 explicit water molecules embedded in the electrostatic field of the remaining 491 molecules give the statistically converged values of 24.4 +/- 0.8 and 28.5 +/- 0.8 ppm, compared with the inferred experimental value of 19 +/- 2 ppm. Considering the simplicity of the PCM over the iterative polarization this is an important aspect and the computational savings point to the possibility of dealing with larger solute molecules. This PCM-MM/QM approach reconciles the simplicity of the PCM model with the reliability of the combined QM/MM approaches.

Optical third-harmonic spectroscopy of the magnetic semiconductor EuTe

EuTe possesses the centrosymmetric crystal structure m3m of rocksalt type in which the second-harmonic generation is forbidden in electric dipole approximation but the third-harmonic generation (THG) is allowed. We studied the THG spectra of this material and observed several resonances in the vicinity of the band gap at 2.2-2.5 eV and at higher energies up to 4 eV, which are related to four-photon THG processes. The observed resonances are assigned to specific combinations of electronic transitions between the ground 4f(7) state at the top of the valence band and excited 4f(6)5d(1) states of Eu(2+) ions, which form the lowest energy conduction band. Temperature, magnetic field, and rotational anisotropy studies allowed us to distinguish crystallographic and magnetic-field-induced contributions to the THG. A strong modification of THG intensity for the 2.4 eV band and suppression of the THG for the 3.15 eV band was observed in applied magnetic field. Two main features of the THG spectra were assigned to 5d(t(2g)) and 5d(e(g)) subbands at 2.4 eV and 3.15 eV, respectively. A microscopic quantum-mechanical model of the THG response was developed and its conclusions are in qualitative agreement with the experimental results.

Optical absorption and electronic band structure first-principles calculations of alpha-glycine crystals

Light absorption of alpha-glycine crystals grown by slow evaporation at room temperature was measured, indicating a 5.11 +/- 0.02 eV energy band gap. Structural, electronic, and optical absorption properties of alpha-glycine crystals were obtained by first-principles quantum mechanical calculations using density functional theory within the generalized gradient approximation in order to understand this result. To take into account the contribution of core electrons, ultrasoft and norm-conserving pseudopotentials, as well as an all electron approach were considered to compute the electronic density of states and band structure of alpha-glycine crystals. They exhibit three indirect energy band gaps and one direct Gamma-Gamma energy gap around 4.95 eV. The optical absorption related to transitions between the top of the valence band and the bottom of the conduction band involves O 2p valence states and C, O 2p conduction states, with the carboxyl group contributing significantly to the origin of the energy band gap. The calculated optical absorption is highly dependent on the polarization of the incident radiation due to the spatial arrangement of the dipolar glycine molecules; in the case of a polycrystalline sample, the first-principles calculated optical absorption is in good agreement with the measurement when a rigid energy shift is applied.

Detection of mechanical and disease stresses in citrus plants by fluorescence spectroscopy

We have investigated the detection of mechanical and disease stresses in citrus plants (Citrus limonia [L.] Osbeck) using laser-induced fluorescence spectroscopy. Due to its economic importance we have chosen to investigate the citrus canker disease, which is caused by the Xanthomonas axonopodis pv. citri bacteria. Mechanical stress was also studied because it plays an important role in the plant's infection by such bacteria. A laser-induced fluorescence spectroscopy system, composed of a spectrometer and a 532 nm 10 mW excitation laser was used to perform fluorescence spectroscopy. The ratio of two chlorophyll fluorescence bands allows us to detect and discriminate between mechanical and disease stresses. This ability to discriminate may have an important application in the field to detect citrus canker infected trees. (c) 2008 Optical Society of America.

Microstructure and mechanical properties of laser-welded joints of TWIP and TRIP steels

With the aim of investigating a laser-welded dissimilar joint of TWIP and TRIP steel sheets, the microstructure was characterized by means of OM, SEM, and EBSD to differentiate the fusion zone, heat-affected zone, and the base material. OIM was used to differentiate between ferritic, bainitic, and martensitic structures. Compositions were measured by means of optical emission spectrometry and EDX to evaluate the effect of manganese segregation. Microhardness measurements and tensile tests were performed to evaluate the mechanical properties of the joint. Residual stresses and XRD phase quantification were used to characterize the weld. Grain coarsening and martensitic areas were found in the fusion zone, and they had significant effects on the mechanical properties of the weld. The heat-affected zone of the TRIP steel and the corresponding base material showed considerable differences in the microstructure and properties. (C) 2009 Elsevier B.V. All rights reserved.

Texture and mechanical properties evolution of a deep drawing medium carbon steel during cold rolling and subsequent recrystallization

Medium carbon steels are mostly used for simple applications; however, new applications have been developed for which good sheet metal formability is required. These types of steels have an inherent low formability. A medium-carbon hot-rolled SAE 1050 steel was selected for this study. It has been cold rolled with thickness reductions varying between 7 and 80%. The samples obtained were used to evaluate the strain hardening curve. For samples with a 50 and 80% thickness reduction, an annealing heat treatment was performed to achieve recrystallization. The material was characterized in the ""as-received"", cold rolled and annealed conditions using several methods: optical metallography, X-ray diffraction (texture), Vickers hardness, and tensile testing. For large thickness reductions, the SAE 1050 steel presented low elongation, less than 2%, and yield strength (YS) and tensile strength (TS) around 1400 MPa. Texture in the ""as-received"" condition showed strong components on the {001} plane, in the < 100 >, < 210 > and (110) directions. After cold rolling, the texture did not present any significant changes for small thickness reductions, however. It changed completely for large ones, where gamma, < 111 >//ND, alpha, < 110 > HRD, and gamma prime, < 223 >//ND, fibres were strengthened. After annealing, the microstructure of the SAE 1050 steel was characterized by recrystallized ferrite and globular cementite. There was little change in the alpha fibre for the 50% reduction, whereas for the 80% reduction, its intensity increased. Both gamma and gamma prime fibres vanished upon annealing for 50 and 80% reductions alike. (c) 2008 Elsevier B.V. All rights reserved.

Medium carbon steel deep drawing: A study on the evolution of mechanical properties, texture and simulations, from cold rolling to the end product

Medium carbon steels are mostly used for simple applications; nevertheless new applications have been developed for which good sheet formability is required. This class of steels has an inherent low formability. A medium carbon hot rolled SAE 1050 steel has been selected for this study. It has been cold rolled with reductions in the 7-80% range. Samples have been used to assess the cold work hardening curve. For samples with a 50 and 80% thickness reduction, an annealing heat treatment has been performed to obtain recrystallization. The material has been characterized in the ""as received"", cold rolled and annealed conditions, using several methods: optical microscopy, X-ray diffraction (texture), Vickers hardness and tensile testing. The 50% cold rolled and recrystallized material has been further studied in terms of sheet metal formability and texture evolution during the actual stamping of a steel toecap that has been used to validate the finite element simulations. (C) 2008 Elsevier B.V. All rights reserved.

Bone Remodeling Adjacent to Morse Cone-Connection Implants with Platform Switch: A Fluorescence Study in the Dog Mandible

Purpose: The aim of this study was to evaluate, through fluorescence analysis, the effect that different interimplant distances, after prosthetic restoration, will have on bone remodeling in submerged and nonsubmerged implants restored with a ""platform switch."" Materials and Methods: Fifty-six Ankylos implants were placed 1.5 mm subcrestally in seven dogs. The implants were placed so that two fixed prostheses, with three interimplant contacts separated by 1-mm, 2-mm, and 3-mm distances, could be fabricated for each side of the mandible. The sides and the positions of the groups were selected randomly. To better evaluate bone remodeling, calcein green was injected 3 days before placement of the prostheses at 12 weeks postimplantation. At 3 days before sacrifice (8 weeks postloading), alizarin red was injected. The amounts of remodeled bone within the different interimplant areas were compared statistically before and after loading in submerged and nonsubmerged implants. Results: Statistically significant differences existed in the percentage of remodeled bone seen in the different regions. Mean percentages of remodeled bone in the submerged and nonsubmerged groups, respectively, were as follows: for the 1-mm distance, 23.0% +/- 0.05% and 23.1% +/- 0.03% preloading and 27.0% +/- 0.03% and 25.2% +/- 0.04% postloading, for the 2-mm distance, 18.2% +/- 0.05% and 18.1% +/- 0.04% preloading and 21.3% +/- 0.07% and 19.9% +/- 0.03% postloading, for the 3-mm distance, 18.3% +/- 0.03% and 18.3% +/- 0.03% preloading and 18.8% +/- 0.04% and 19.8% +/- 0.04% postloading, for distal-extension regions, 16.6% +/- 0.02% and 17.4% +/- 0.04% preloading and 17.0% +/- 0.04% and 18.4% +/- 0.04% postloading. Conclusions: Based upon this animal study, loading increases bone formation for submerged or nonsubmerged implants, and the interimplant distance of 1 mm appears to result in more pronounced bone remodeling than the 2-mm or 3-mm distances in implants with a ""platform switch."" INT J ORAL MAXILLOFAC IMPLANTS 2009;24:257-266

Theoretical investigation of electronic and optical properties of andalusite within density functional theory

The electronic and optical properties of andalusite were studied by using quantum-mechanical calculations based on the density functional theory (DFT). The electronic structure shows that andalusite has a direct band gap of 5.01 eV. The complex dielectric function and optical constants, such as extinction coefficient, refractive index, reflectivity and energy-loss spectrum, are calculated. The optical properties of andalusite are discussed based on the band structure calculations. It is shown that the O-2p states and Al-3s states play a major role in optical transitions as initial and final states, respectively. (C) 2010 Elsevier Ltd. All rights reserved.

UV optical absorption spectra analysis of beryl crystals from Brazil

The spectral decomposition analysis was applied to the optical absorption spectra of green and colorless beryl crystals from the Brazilian Eastern Pegmatitic province in the natural state, Submitted to heat treatment and irradiated with UV light The attributions of the lines were made taking into account highly accurate quantum mechanical calculations The deconvolution of the green beryl spectra revealed four lines, two of them around 12,000 cm(-1) (1 5eV) and two of them around 34,000 cm(-1) (4.2 eV) attributed to Fe(2+) and Fe(3+), respectively The deconvolution of the colorless beryl spectra without any treatment, after heating and for the same heat treatment followed by UV light irradiation revealed five lines The analysis of ratio relations showed that the lines at 36,400 cm(-1) (4.5 eV) and 41,400 cm(-1) (5 1 eV) belongs to a single defect attributed to a silicon dangling bond defect (=Si). Discussions and comparison with reported defects in quartz have supported the allocation of the lines at 61,000 cm(-1) (7.6 eV) and 43,800 cm(-1) (5 4 eV) to diamagnetic oxygen vacancy defect ( Si-Si ) and unrelaxed ( Si Si ) defect, respectively Finally, the line at 39.100 cm(-1) (4.8 eV), quite polarized along the c-axis, was attributed to a (Fe(2+) OH(-)) defect in the structural channels (C) 2009 Elsevier B V All rights reserved

Electronic structure and optical properties of BaMoO(4) powders

Barium molybdate (BaMoO(4)) powders were synthesized by the co-precipitation method and processed in microwave-hydrothermal at 140 degrees C for different times. These powders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis) absorption spectroscopies and photoluminescence (PL) measurements. XRD patterns and FT-Raman spectra showed that these powders present a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 850.4 cm(-1), which is associated to the Mo-O antisymmetric stretching vibrations into the [MoO(4)] clusters. UV-vis absorption spectra indicated a reduction in the intermediary energy levels within band gap with the processing time evolution. First-principles quantum mechanical calculations based on the density functional theory were employed in order to understand the electronic structure (band structure and density of states) of this material. The powders when excited with different wavelengths (350 nm and 488 nm) presented variations. This phenomenon was explained through a model based in the presence of intermediary energy levels (deep and shallow holes) within the band gap. (C) 2009 Elsevier B.V. All rights reserved.

Effect of Different Solvent Ratios (Water/Ethylene Glycol) on the Growth Process of CaMoO(4) Crystals and Their Optical Properties

In this paper, calcium molybdate (CaMoO(4)) crystals (meso- and nanoscale) were synthesized by the coprecipitation method using different solvent volume ratios (water/ethylene glycol). Subsequently, the obtained suspensions were processed in microwave-assisted hydrothermal/solvothermal systems at 140 degrees C for 1 h. These meso- and nanocrystals processed were characterized by X-ray diffraction (X R I)), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR). ultraviolet visible (UV-vis) absorption spectroscopies, held-emission gun scanning electron microscopy (FEG-SEM). transmission electron microscopy (TEM). and photoluminescence (PL) measurements. X RI) patterns and FT-Raman spectra showed that these meso- and nanocrystals have a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 827 cm(-1), which is associated with the Mo-O anti-symmetric stretching vibrations into the [MoO(4)] clusters. FEG-SEM micrographs indicated that the ethylene glycol concentration in the aqueous solution plays an important role in the morphological evolution of CaMoO(4) crystals. High-resolution TEM micrographs demonstrated that the mesocrystals consist of several aggregated nanoparticles with electron diffraction patterns of monocrystal. In addition, the differences observed in the selected area electron diffraction patterns of CaMoO(4) crystals proved the coexistence of both nano- and mesostructures, First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were employed in order to understand the band structure find density of states For the CaMoO(4). UV-vis absorption measurements evidenced a variation in optical band gap values (from 3.42 to 3.72 cV) for the distinct morphologies. The blue and green PI. emissions observed in these crystals were ascribed to the intermediary energy levels arising from the distortions on the [MoO(4)] clusters clue to intrinsic defects in the lattice of anisotropic/isotropic crystals.

The low-lying electronic states of BeP: a reliable and accurate quantum mechanical prediction

A very high level of theoretical treatment (complete active space self-consistent field CASSCF/MRCI/aug-cc-pV5Z) was used to characterize the spectroscopic properties of a manifold of quartet and doublet states of the species BeP, as yet experimentally unknown. Potential energy curves for 11 electronic states were obtained, as well as the associated vibrational energy levels, and a whole set of spectroscopic constants. Dipole moment functions and vibrationally averaged dipole moments were also evaluated. Similarities and differences between BeN and BeP were analysed along with the isovalent SiB species. The molecule BeP has a X (4)Sigma(-) ground state, with an equilibrium bond distance of 2.073 angstrom, and a harmonic frequency of 516.2 cm(-1); it is followed closely by the states (2)Pi (R(e) = 2.081 angstrom, omega(e) = 639.6 cm(-1)) and (2)Sigma(-) (R(e) = 2.074 angstrom, omega(e) = 536.5 cm(-1)), at 502 and 1976 cm(-1), respectively. The other quartets investigated, A (4)Pi (R(e) = 1.991 angstrom, omega(e) = 555.3 cm(-1)) and B (4)Sigma(-) (R(e) = 2.758 angstrom, omega(e) = 292.2 cm(-1)) lie at 13 291 and 24 394 cm(-1), respectively. The remaining doublets ((2)Delta, (2)Sigma(+)(2) and (2)Pi(3)) all fall below 28 000 cm(-1). Avoided crossings between the (2)Sigma(+) states and between the (2)Pi states add an extra complexity to this manifold of states.

Comparison of physical and mechanical properties of microwave-polymerized acrylic resin after disinfection in sodium hypochlorite solutions

This study evaluated the color stability, surface roughness and flexural strength of a microwave-polymerized acrylic resin after immersion in sodium hypochlorite (NaOCl), simulating 20 min of disinfection daily during 180 days. Forty disk-shaped (15 x 4 mm) and 40 rectangular (65 x 10 x 3 mm) specimens were prepared with a microwave-polymerized acrylic resin (Onda-Cryl). Specimens were immersed in either 0.5% NaOCl, 1% NaOCl, Clorox/Calgon and distilled water (control). Color measurements were determined by a portable colorimeter. Three parallel lines, separated by 1.0 mm, were registered on each specimen before and after immersion procedures to analyze the surface roughness. The flexural strength was measured using a 3-point bending test in a universal testing machine with a 50 kgf load cell and a crosshead speed of 1 mm/min. Data were analyzed statistically by ANOVA and Tukey's test (?=0.05). There was no statistically significant differences (p>0.05) among the solutions for color, surface roughness and flexural strength. It may be concluded that immersion in NaOCl solutions simulating short-term daily use during 180 days did not influence the color stability, surface roughness and flexural strength of a microwave-polymerized acrylic resin.