Structure,electronic,and nonlinear optical properties of superalkaline M_(3)O(M=Li,Na)doped cyclo[18]carbon

Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.

Synthesis of Poly (3-acetylpyrrolyl methine) with Azobenzene Side Groups and Study on Its Third-order Nonlinear Optical Property

A novel soluble π-conjugated polymer, poly [（3-acetylpyrrole-2, 5-diyl） p-（N, N-dimethylamino） azobenzylidene] （PAPDMAABE）, was synthesized by condensation of 3-acetylpyrrole with 4-aldehyde-4＇-dimethylaminoazobenzene （ADMAA）. The chemical structure of PAPDMAABE was characterized by Fourier transform infrared spectroscopy （FTIR）, ^1H-NMR, and UV-Vis-NIR spectra. Transmission electron microscope （TEM） analysis for PAPDMAABE indicates that part of PAPDMAABE is in crystal state, due to the short-range order of the polymer. Thermogravimetric analysis （TGA） curve shows that the polymer has good thermal stability and its decomposition temperature is 248℃. The optical band gap of PAPDMAABE obtained from the optical absorption spectrum is about 1.73 eV. The resonant third-order nonlinear optical property of PAPDMAABE at 532 nm was studied using degenerate four-wave mixing （DFWM） technique. The resonant third-order nonlinear optical susceptibility of the polymer is about 7.48×10^-8 esu.

On the Role of Bond Function in Nonlinear Optical Property Calculations for HF,HCI,LiH,H_2O and NH_3

Dond function basis sets have been used to calculate the molecular nonlinear optical properties which include hyperpolarizability βo , polarizability ao , and dipole moment μo for six molecules. The calculations at the fourth-order Moller-Plesset approximation (MP4) have recovered more than 90% of the experimental values βo , comparecl to that as low as 75% by the other authors. The calculated values of αo and iuo are also in good agreement with those of experiments and superior to that from other work. It is shown that the bond functions improve the calculated results at SCF level and especially at the level of the correction of electronic correlation (MP2 and MP4).

NONLINEAR OPTICAL PROPERTY OF para-DISUBSTITUTED BENZYLIDENE-ANILINE DERIVATIVES

Forty para-disubstituted benzylidene-aniline derivatives were synthesized,and their second harmonic generation(SHG)efficiency was measured by the Kurtz powder technique.The effect of the electronic property and the position of the substituents on powder SHG efficiency was studied.

Synthesis of Poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] and Its Third-order Nonlinear Optical Property

A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] (POPNBE), was synthesized by a five-step reaction. As a result of introducing a long acyl to pyrrole at 3-position, the polymer can be easily solved in polar solvents and be processed into films. The chemical structures of the intermediates and POPNBE were characterized by FTIR, 1H NMR, and UV-Vis-NIR spectrometries. The absorption band in the range of 400-600 nm in the UV-Vis-NIR spectrum is due to the π-π * band gap transition. The optical band gap of POPNBE obtained from the optical absorption is about 1.72 eV. The resonant third-order nonlinear optical property of POPNBE at 532 nm was studied by using the degenerate four-wave mixing(DFWM) technique. The resonant third-order nonlinear optical susceptibility of POPNBE is about 3.42×10 -8 esu.

Crystal Structure and Third-order Nonlinear Optical Property Studies on Copper(Ⅱ) Complex Containing NS Donor Ligand

A novel Schiff base ligand (HL) derived from S-methyldithiocabazate and pmethoxylbenzaldehyde was prepared and characterized. The Schiff base ligand acts as a single negatively charged bidentate ligand fondng D-M-D type comPlex (D=donor, M=metal). Single crystal X-ray diffraction analysis of the copper(Ⅱ) complex established that the geometry around Cu (Ⅱ) is square-planar with two equivalent M-N and M-S bonds. The two phenyl rings and the coordinated plane are almost in one plane fotheng an electronic delocalization system. Their thirdorder response was also studied.

Electronic Absorption Spectra and Third-Order Nonlinear Optical Property of Dinaphtho[2,3-b:2’,3’-d]Thiophene-5,7,12,13- Tetraone (DNTTRA) and Its Phenyldiazenyl Derivatives: DFT Calculations

Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 107 atomic units (10-33 esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH3)2 or -NHCH3) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.

RANDOM MICROSTRUCTURE FINITE ELEMENT METHOD FOR EFFECTIVE NONLINEAR PROPERTIES OF COMPOSITE MATERIALS

Some theoretical methods have been reported to deal with nonlinear problems of composite materials but the accuracy is not so good. In the meantime, a lot of linear problems are difficult to be managed by the theoretical methods. The present study aims to use the developed method, the random microstructure finite element method, to deal with these nonlinear problems. In this paper, the random microstructure finite element method is used to deal with all three kinds of nonlinear property problems of composite materials. The analyzed results suggest the influences of the nonlinear phenomena on the effective properties of composite materials are significant and the random microstructure finite element method is an effective tool to investigate the nonlinear problems.

All-optical switching and nonlinear optical properties of HBT in ethanol solution

This paper demonstrates an all-optical switching model system comprising a single pulsed pump beam at 355 nm and a CW He-Ne signal beam at 632.8 nm with 2-（2＇-hydroxyphenyl）benzothiazole （HBT） in ethanol solution. The origins of the optical switching effect were discussed. By the study of nonlinear optical properties for HBT in ethanol solvent, this paper verified that the excited-state intramolecular proton transfer （ESIPT） effect of HBT and the thermal effect of solvent worked on quite different time scales and together induced the change of the refractive index of HBT solution, leading to the signal beam deflection. The results indicated that the HBT molecule could be an excellent candidate for high-speed and high-sensitive optical switching devices.

New Application of bond Function Basis Sets──ab initio Calculations of Nonlinear Optical Properties

On the basis of adding the bond functions (3s 3p 2d) to the basis sets 6-311G ( 2d 2p ) for increasing the efficiency of the basis sets , we have carried out the MP2 calculations of nonlinear optical properties includintg dipole moment uo,polarizibili- ty ao and hyperpolarizability , for CH4-nFn (n = 1 , 2 , 3). The results are in good a- greement with those of experimentsl The roles of the bond functions in the calcula- tions are shown , i. e., the improved values of the properties are about 2%-7% at the SCF level and about 6%-30% at the correlated level (MP2). It is shown that the more important role of the bond functions in calculating is the im- provement of the effects of the corrections of electronic correlations and the increase of the effects is in the order of. In addition , it is also shown that the cal-, culated value of a property does not change with the bond-function location in our calculations except for the regions close to the nuclei in a molecule.

The Third-Order Nonlinear Optical Properties in Cobalt-Doped ZnO Films

We quantitatively investigate the third-order optical nonlinear response of Co-doped ZnO thin films prepared by magnetron sputtering using the Z-scan method. The two-photon absorption and optical Kerr effect are revealed to contribute to the third-order nonlinear response of the Co-doped ZnO films. The nonlinear absorption coefficient β is determined to be approximately 8.8 × 10-5 cm/W and the third-order nonlinear susceptibility X（3） is 2.93 × 10-6 esu. The defect-associated energy levels within the band gap are suggested to be responsible for the enhanced nonlinear response observed in Co-doped ZnO films.

Theoretical Investigation on the Second-order Nonlinear Optical Properties of Chiral Amino Acid Zinc(Ⅱ) Porphyrins

Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipola- rizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic χ (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.

UV-Vis Spectrum and the Third-order Nonlinear Optical Properties of the Chiral Camphorderived β-diketonate Platinum Complexes

UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.

Improvement of sintering,nonlinear electrical,and dielectric properties of ZnO-based varistors doped with TiO2

The effects of TiO2 on sintering and nonlinear electrical properties of（98.5-x）ZnO–0.5MnO2–0.5Co2O3-0.5Bi2O3–xTiO2（x = 0.3,0.5,0.7,0.9 mol%） ceramic varistors prepared by the ceramic technique are investigated in this work.The optimum sintering temperature of the prepared samples is deduced by determining the firing shrinkage and water absorption percentages.The optimum sintering temperature is found to be 1200℃,at which each of the samples shows a maximum firing shrinkage and minimum water absorption.Also minimum water absorption appears in a sample of x = 0.9 mol%.Higher sintering temperature and longer sintering time give rise to a reduction in bulk density due to the increased amount of porosity between the large grains of ZnO resulting from the rapid grain growth induced by the liquid phase sintering.The crystal size of ZnO decreases with increasing TiO2 doping.The addition of TiO2 improves the nonlinear coefficient and attains its maximum value at x = 0.7 mol% of TiO2,further addition negatively affects it.A decrease in capacitance consequently in the dielectric constant is recorded with increasing the frequency in a range of 30 kHz–200 kHz.The temperature and composition dependences of the dielectric constant and AC conductivity are also studied.The increase of temperature raises the dielectric constant because it increases ionic response to the field at any particular frequency.

Linear and nonlinear optical properties of Sb-doped GeSe_2 thin films

Sb-doped GeSe2 chalcogenide thin films are prepared by the magnetron co-sputtering method. The linear optical properties of as-deposited films are derived by analyzing transmission spectra. The refractive index rises and the optical band gap decreases from 2.08 eV to 1.41 eV with increasing the Sb content. X-ray photoelectron spectra further confirm the formation of a covalent Sb--Se bond. The third-order nonlinear optical properties of thin films are investigated under femtosecond laser excitation at 800 nm. The results show that the third-order nonlinear optical properties are enhanced with increasing the concentration of Sb. The nonlinear refraction indices of these thin films are measured to be on the order of 10-18 m2/W with a positive sign and the nonlinear absorption coefficients are obtained to be on the order of 10-10 m/W. These excellent properties indicate that Sb-doped Ge-Se films have a good prospect in the applications of nonlinear optical devices.

Second-order Nonlinearities of CdS Nanoparticles Studied by Hyper-Rayleigh Scattering Technique

A series of CdS nanoparticles with different surfaces were prepared by colloidal chemical method and reverse micelle method. Their second-order nonlinear optical (NLO) properties were experimentally studied in solution by newly developed hyper-Rayleigh scattering (HRS) technique. The results show that 'per particle' first-order hyperpolarizability beta values are sensitive To the synthetic method and the surface chemical modification.

THIRD ORDER NONLINEAR OPTICAL PROPERTIES OF PERNIGRANILINE SOLUTION IN CONCENTRATED SULFURIC ACID

The fully oxidized state of polyaniline (PANI), pernigraniline (PN), was synthesized by oxidation of the emeraldine base form of PAM dissolved in NMP solvent with m-chloroperoxybenzoic acid. The resulted PN was characterized by FTIR and UV-Visible spectra. The third-order nonlinear optical properties of PN in concentrated sulfuric acid (PN/H2SO4) were measured by a degenerated four wave mixing (DFWM) method. The results obtained suggest that the soliton-pair intermediate state associated with the degenerated state does not play a major role in the third order nonlinear optical properties of PANI.

Theoretical Investigation on Structures and Second-order Nonlinear Optical Properties of (Thiophene) Manganese Tricarbonyl Cations

The structures of several recently reported organometallic NLO chromophores, (thio-phene) manganese tricarbonyl cations, were fully optimized at the DFT non-local (GGA) level. The calculated results show that the fragments 2-SC4H3CH=CHC6H4-R in these organometallic chromophores are not planar with dihedral angles of 42.2~59.8 between two aromatic rings, which are different from those of uncoordinated counterparts. Based on the DFT geometry opti-mization, the second-order nonlinear optical polarizabilities were calculated by using RPA method. The calculated results indicate that incorporation of +3Mn(CO) unit with thiophene leads to a sub-stantial increase in the second-order polarizability (b).

Synthesis of Imidazole Derivatives for Their Second-order Nonlinear Optics

The design and the synthesis of two conjugated donor acceptor imidazole derivatives(1, 2) were carried out for second order nonlinear optics. The thermal properties, the transparency and second order nonlinear optical properties of the molecules were investigated. The experimental results indicate that a good nonlinearity transparency thermal stability trade off is achieved for them.

Preparation of Organic Nanoparticle Colloids by Laser Ablation and Their Nonlinear Optical Properties

Suspension of micrometer-sized 1,4-bis（4-methylstyryl）benzene（p-MSB） was converted into colloidal nanocrystal solution by irradiation with an femtosecond laser（800 nm, 1 kHz）. The prepared nanocrystals were rectangular with ca. 100 nm in size. The same crystal structure as that of bulk crystals was confirmed by X-ray diffraction measurement. UV-Vis spectra and emission spectra of the nanoparticle dispersions in dichloromethane（poor solvent） were examined. The nanocrystal exhibits large quantum yield（89%）. The nonlinear optical properties of the nanocrystals were further studied by Z-scan technique with femtosecond laser duration of 120 fs at a wavelength of 800 nm. The results show that the nanocrystals exhibit strong nonlinear absorption.