Investigation of the polyetherketone guest–host DR1/PEK-c polymer films by real-time monitoring of the second-harmonic generation

The real-time monitoring of the second-harmonic generation (SHG) was used to optimize the poling condition and to study the nonlinear optical (NLO) properties of the polyetherketone (PEK-c) guest–host polymer films. The high second-order NLO coefficient χ₃₃⁽²⁾=11.02 pm/v measured at 1.064 μm was achieved when the weight percent of DR1 guest in the polymer system is 20%. The NLO activity of the poled DR1/PEK-c polymer film can maintain more than 80% of its initial value when temperature is under 100°C, and the normalized second-order NLO coefficient can maintain more than 85% after 2400 s at 80°C.     

The structural, optical, and dielectric spectroscopy studies of novel ZnO–As2O3 glass system with Sb2O3 as additive

ZnO–As₂O₃–Sb₂O₃ glasses of varying concentrations of Sb₂O₃ with ZnO (ranging from 5 to 45 mol%) are prepared. A number of studies, including differential thermal analysis, and study of spectroscopic properties (viz., optical absorption and IR spectra) and dielectric properties (constant ε′, loss tan δ and ac conductivity σ_ac) over a wide range of frequency and temperature of these glasses are carried out. Analyses of the results of these investigations have indicated that the glasses containing higher concentrations of Sb₂O₃ are more suitable for non-linear optical (NLO) applications.     

Infrared absorption-edges of molecular nonlinear optical crystals: an <Emphasis Type="Italic">ab initio</Emphasis> calculation

A theoretical model suitable for calculating infrared absorption-edges of molecular nonlinear optical (NLO) crystals is introduced from high-level calculations of molecular vibrational spectra. The model is useful for elucidating the relationship between the molecular vibration and macroscopic absorption edges on the IR side of organic nonlinear optical crystals. The first-principle ab initio method carries out the calculations of IR absorption-edges of several typical molecular NLO crystals. These molecular NLO crystals include urea, 2-methyl-4-nitroaniline (MNA), meta-dinotrobenzene (MDNB), 3-methyl-4-methooxy-4^′-nitrostilbene (MMONS), and 3-hydroxyl-4^′-nitrostilbene (HMONS). The calculated results are compared with the measurements and good agreement is found between them. The experimentally unknown values of IR absorption-edges of some new synthesized crystals are predicted. The theoretical analyses of the structural origins of IR absorption cut-offs are discussed. The results are helpful for the molecular simulation and design of potential infrared molecular NLO crystals. Received: 9 April 2002 / Accepted: 18 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +86-591/3714946, E-mail: wkc@ms.fjirsm.ac.cn     

Infrared vibrational spectra of -histidinium dihydrogen orthophosphate orthophosphoric acid (LHP)

The entire vibrational spectrum of a single crystal of -histidinium dihydrogen orthophosphate orthophosphoric acid (LHP) was studied by infrared (IR) spectroscopy from 10 up to 4000 cm⁻¹. The polarized infrared (IR) reflectivity spectra were measured between 7 and 250 K, in the frequency range 10–600 cm⁻¹. From the IR spectral analysis, the phonon modes were classified within their symmetry species, and their longitudinal (LO) and transversal (TO) optical frequencies were calculated. A tentative assignment of the various internal modes observed in the transmissivity spectrum of LHP, between 300 and 4000 cm⁻¹, is proposed. The present study did not reveal any low-temperature structural phase transition.     

Determination of the macroscopic optical properties for the NAEC/PEK-c guest–host polymer films

The polyetherketone (PEK-c) guest–host polymer films doped with (4′-nitro)-3-azo-9-ethyl-carbazole (NAEC) were prepared. The films were poled by corona-onset poling at elevated temperature (COPET). The orientational order parameter of the chromophores NAEC in poled polymer film was determined by measuring the absorption spectra of the films before and after being poled. By using the two-level model, the measured dispersion of the refractive index of the polymer film, and the dispersion of the first hyperpolarizability of chromophore NAEC, the dispersion of the macroscopic second-order nonlinear optical (NLO) and linear electro-optic (EO) coefficients was evaluated for the NAEC/PEK-c guest–host polymer film.     

A novel CO2 gas analyzer based on IR absorption

Carbon dioxide (CO₂) gas analyzer can be widely used in many fields. A novel CO₂ gas analyzer based on infrared ray (IR) absorption is presented sufficiently in this paper. Applying Lambert–Beer Law, a novel space-double-beam optical structure is established successfully. The optical structure includes an IR source, a gas cell, a bandpass filter with a transmission wavelength at 4.26 μm, another bandpass filter with a transmission wavelength at 3.9 μm, and two IR detectors. Based on Redial Basic Function (RBF) artificial neural network, the measuring model of IR CO₂ analyzer is established with a high accuracy. A dynamic compensation filter is effectively designed to improve the dynamic characteristic of the IR CO₂ analyzer without gas pump. The IR CO₂ analyzer possesses the advantages of high accuracy and mechanical reliability with small volume, lightweight, and low-power consumption. Therefore, it can be used in such relevant fields as environmental protection, processing control, chemical analysis, medical diagnosis, and space environmental and control systems.     

Development of a tunable IR lidar system

A differential absorption lidar system (DIAL) based on a continuously tunable optical parametric amplifier (OPA) pumped by a Nd : YAG laser (200 mJ at λ=355 nm) operating at a maximum pulse repetition rate of 100 Hz has been developed. The system provides continuously tunable coherent radiation in the Visible–near IR range (0.4–2.5 μm), allowing to perform DIAL measurements in a spectral region where most of atmospheric constituents and pollutants display absorption lines. The spectral width of the OPA system is line-narrowed by using a master oscillator dye laser as seeder, achieving a linewidth of 0.04 cm⁻¹ (FWHM), a spectral purity larger than 99% and a frequency stability better than 1 pm h⁻¹, with an output energy in the IR of 1–10 mJ. The OPA system was used to perform DIAL measurements in the lower troposphere. Preliminary results in terms of water vapor content and aerosol backscattering profiles are presented and discussed.     

Simultaneous oscillation on UV and IR transitions of the copper ion laser

Simultaneous oscillation of UV (248–270 nm) and IR lines (773–785 nm) in the copper ion laser with helical hollow cathode has been observed using high reflectivity combination mirrors. The output power characteristics of these laser lines are measured as functions of the discharge current and fill-gas pressure. A total laser power of about 100 mW with equal UV and IR contributions was obtained.     

Structural and nonlinear optical properties of cross‐conjugated system benzophenone thiosemicarbazone: a vibrational spectroscopic study

The nonlinear optical (NLO) compound of interest benzophenone thiosemicarbazone (BTSC) was grown and the molecular structure generated with the aid of density functional theory (DFT). FT‐Raman and IR spectra were recorded and analyzed. The harmonic wavenumbers and IR and Raman intensities were computed with the B3LYP method. The observed vibrational wavenumbers were compared with the calculated results. The assignments of the experimental spectra were made with the help of normal coordinate analysis (NCA) following the scaled quantum mechanical force field (SQMFF) methodology. The electronic structure of the most important molecular fragments is described in terms of natural bond orbital (NBO) analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Temperature field modeling during multi-modes CO2 laser irradiation of human enamel

We examine the temperature fields of human enamel [Yu D, Fox JL, Hsu J, Lynn Powell G, Higuchi WI. Computer simulation of surface temperature profiles during CO₂ laser irradiation of human enamel. Opt Eng 1993; 32(2)] during multi-modes CO₂ laser irradiation. For this we use the integral transform method as well as direct and inverse Laplace transform [Oane M, Sporea D. Temperature profiles modeling in IR optical components during high power laser irradiation. Infrared Phys Technol 2001; 42(1): 31–40; Oane M, Sporea D. Study of heat transfer in IR optical components during CO₂ laser irradiation. Proc SPIE 2001; 4430: 898–904; Oane M. Mathematical modeling of the thermal field distributions in solids under multiple laser irradiations. Proc SPIE 2003; 5227: 329–34; Oane M, Apostol I, Timcu A. Temperature field modeling in laser heated metals for laser cleaning of surfaces. Proc SPIE 2003; 5227: 323–8]. The enamel block is modeled as homogeneous cylinder in three dimensions. Results indicate that (i) the thermal field depends on multi-modes structure; (ii) heat transfer coefficient plays an important role in temperature distribution.     

Second harmonic generation in In2O3–SiON films doped by Al and Sn

Photoinduced optical and second-order non-linear optical effects in the interfaces separating In₂O₃–SiON (O/N ratio equals 1) films doped with A1, Sn and glass substrates were investigated using the photoinduced optical second harmonic generation. The photoinduced effective second-order optical susceptibility d_eff (at λ=1.76 μm) shows a good correlation with the linear optical susceptibility, particularly with the shift of the absorption edge. The maximal response of the photoinduced optical response signal was observed for the pump–probe delaying time of 34 ps. The performed experimental measurements indicate that the observed effects are mainly caused by the interface potential gradients on the border glass–In₂O₃–SiON film and by additional polarization due to insertion of the Al and Sn atoms. The observed phenomenon may be proposed as a sensitive tool for investigation of thin semiconducting interfacial layers and simultaneously such films may be used as materials for non-linear optical devices.     

Electronic and structural effects on the nonlinear optical behavior in π‐conjugated structure bis(4‐nitrophenyl) carbonate: a vibrational spectroscopic approach

Fourier transform (FT)‐Raman and infrared (IR) spectra of the nonlinear optical (NLO) material bis(4‐nitrophenyl) carbonate were recorded and analyzed. The geometry, first hyperpolarizability and harmonic vibrational wavenumbers were calculated with the help of Becke3–Lee–Yang–Parr density functional theory method. The detailed interpretation of the vibrational spectra was carried out with the aid of normal coordinate analysis following the scaled quantum mechanical force field methodology. The second‐order NLO properties of the molecule were studied by the Kurtz and Perry powder reflection technique. Stability of the molecule arising from hyperconjugative interactions leading to its NLO activity and charge delocalization were analyzed using natural bond orbital analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

First order molecular hyperpolarizabilities and intramolecular charge transfer from the vibrational spectra of NLO material: ethyl‐3‐(3, 4‐dihydroxyphenyl)‐2‐propenoate

As part of the efforts for the design of new organic nonlinear optical(NLO) materials with high efficiency for present day technological requirements, a comprehensive investigation on the intramolecular charge transfer(CT) of an efficient π‐conjugated potential push–pull NLO chromophore, ethyl‐3‐(3,4‐dihydroxyphenyl)‐2‐propenoate(EDP) to a strong electron‐acceptor group through the π‐conjugated bridge has been carried out from their vibrational spectra. The first hyperpolarizabilities of caffeic derivatives are investigated by ab initio method. The NLO efficiency is experimentally measured by powder efficiency experiment. The strongest vibrational modes contributing to the electro‐optic effect from the simultaneous infrared(IR) and Raman activities of the ring CC stretching modes, in‐plane deformation modes, and the umbrella mode of the methyl groups have been identified and analyzed unambiguously. The influence of electronic effects, hyperconjugation and backdonation, on the C H stretching vibrations of both methyl and methylene groups causing the decrease of stretching wavenumbers and IR intensities has been extensively investigated. Copyright © 2009 John Wiley & Sons, Ltd.     

Sum-frequency generation at electrochemical interfaces: Cyanide vibrations on Pt(111) and Pt(110)

We use optical sum-frequency generation to investigate the stretching vibrations of cyanide (CN^–) molecules chemisorbed from aqueous electrolytes on single-crystalline Pt(111)- and Pt(110)-electrode surfaces. For clean and well-ordered Pt(111) electrodes, a single vibrational band between 2080 and 2150 cm^–1 with a nonlinear frequency dependence on the potential is observed and assigned to the CN stretching vibration of chemisorbed cyanide. A second band between 2145 and 2150 cm^–1 with very weak potential dependence appears on a surface which was subjected to oxidation-reduction cycles and is attributed to cyanide associated with a microscopically disordered surface. This assignment is supported by preliminary results for a Pt(110) single-crystal electrode. On a well-ordered (110) surface a single and potential-dependent cyanide vibration between 2070 and 2112 cm^–1 is observed. After oxidation of the cyanide and readsorption, this band is replaced by a higher frequency band at 2144 cm^–1 which is essentially not potential-dependent. Occasionally, additional vibrational bands at lower frequencies not reported in corresponding IR studies are observed on Pt(111).Paper presented at the 129th WE-Heraeus-Seminar on Surface Studies by Nonlinear Laser Spectroscopies, Kassel, Germany, May 30 to June 1, 1994     

Infrared and Raman spectroscopies of InP/II–VI core-shell nanoparticles

We use infrared (IR) and Raman spectroscopies to investigate the optically active phonon modes in InP nanoparticles and InP/II–VI core-shell nanoparticles fabricated by similar colloidal chemistry methods. The IR transmission spectra of several InP nanoparticle samples exhibit a common absorption feature, which we assign to the Fröhlich mode. The Raman results for the same samples show transverse and longitudinal optical phonon peaks, and scattering strength in between due to surface optical (SO) modes. Infrared spectra of the InP/ZnSe core-shell nanoparticles () exhibit three absorption features, one due to the InP core, and the others associated with the ZnSe shell layer. Raman measurements (12–292 K) also show three phonon-related peaks, whose intensities vary sharply with temperature. The frequencies of the IR and Raman lines are in approximate accord with dielectric continuum theory.     

CCD-camera based high sensitivity TL/OSL-spectrometer

A high sensitivity TL/OSL-spectrometer has recently been built at the Freiberg Luminescence Dating Laboratory. It detects luminescence over a range of 200–800 nm simultaneously with a grating spectrograph and an attached liquid-nitrogen cooled CCD-array. The completely computer-controlled system allows free user defined measurement cycles in a temperature range of 20–700°C and optical stimulation from UV to IR with monochromatic light from a 200 W mercury lamp. The general construction of the apparatus and examples of spectra are presented.     

Optical Properties of [(CH3)2NH2]5Cd3Cl11 Crystals in the Region of their Phase Transitions

A sequence of phase transitions in the [(CH₃)₂NH₂]₅Cd₃Cl₁₁ (DMACC) crystal has been verified based on the study of temperature dependences of the optical birefringence and the data of piezooptical investigations. Absorption spectra in the visible and near-UV regions and IR reflection spectra in the 200–2000-cm^–1 region have been obtained. Phase transitions at temperatures of 179.5, 151, and 120 K have been detected. For all the phases of the DMACC crystal, the optical absorption edge obeys Urbach's empirical rule. It is shown that the phonons corresponding to the internal vibrations of the (Cd₃Cl₁₁)^5– polyhedron participate in the edge formation.     

Calculation of multilayer heat-reflecting screens

A recursive calculation of reflection and transmission coefficients based on classical Fresnel formulas is performed for dielectric-metal-dielectric-type screens. The metal is assumed to be silver, while the dielectric layer is formed of semiconductors or dielectrics with index of refraction varying from n = 1.8 to n = 2.6. A BÉSM-6 computer was used to calculate various optical characteristics of such screens in the visible and IR ranges. It is shown that systems with n = 2.2–2.6 show the greatest promise for use as heat reflecting coatings.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 86–91, February, 1984.     

Effect of thermal treatment on the nonlinear optical response and stability of hybrid inorganic-organic films

Hybrid inorganic-organic second-order nonlinear optical (NLO) materials have been obtained through hydrolysis and co-condensation between tetraethyl silicate (TEOS), Vinyltriethoxysilane (VTES) and an alkoxysilane dye (ICTES-DR1). The hybrid materials showed a thermal stability up to 306 °C in thermogravimetric analysis (TGA) thermograms and no visible glass transition temperature (T_g) was observed in the range 50-200 °C in differential scanning calorimetry (DSC) thermograms. The poling profiles of the hybrid films were investigated by using the in situ second harmonic generation (SHG) measurement. The thermal stability of the second order NLO properties of the poled films were also investigated by the in situ SHG intensity probing. It has been shown that the NLO response and its thermal stability were strongly dependent on the thermal pretreatment of the films.     

NLO characteristics of D-π-A coumarin-thiophene bridged azo dyes by Z-scan and DFT methods

ABSTRACT

The structural, electronic, intramolecular charge transfer (ICT) and nonlinear optical (NLO) properties of the donor-π-acceptor (D-π-A) azo linked dyes bearing coumarin thiophene bridge with different acceptors were inspected by Z-scan and DFT methods. The dye 3a exhibits bathochromic absorption maxima (649 and 650?nm) in the near IR region in DMF and DMSO. The dye 3a holds low HOMO–LUMO gap elucidated by CV and DFT indicating strong ICT character. The thermal stability is high for 3a and it shows enhanced NLO property by Z-scan and DFT methods as predicted in both global and range-separated hybrid functionals. The molecular geometry was optimised using B3LYP/6-311?+?g(d,p). The ICT characteristics are correlated with NLO properties obtained by Z-scan and DFT techniques.