A Theoretical Study of Nonlinear Second-Order Optical Properties of Substituted Silanes

On the basis of ZINDO method and according to the sum over states(SOS) expression, the program is devised for the calculation of nonlinear second order optical susceptibilites β ijk and studying how different substituents on the phenyl ring attached to the atom silicon influence on the nonlinear second order optical properties of substituted silane series of molecules. The properties of (CH 3) 3Si? ?has been studied particularly. The effect of the length of silica chains on the calculated values has been studied too. The regularity summarized from the calculated results has been explained micromechanically.

An 8-Connected Chiral Lanthanide Metal-organic Framework Constructed from Naturally Camphoric Acid:Crystal Structure,Vibrational Circular Dichroism Spectroscopy and Second-order Nonlinear Optical Effect

A chiral lanthanide metal-organic framework based on enantiopure camphoric acid （D-H2cam）, [Nd3（D-cam）8（H2O）4Cl]n （1）, has been synthesized and characterized by single-crystal X-ray structural analysis, elemental analysis, IR, thermal gravimetric, and X-ray powder diffraction. Crystal data for the title compound are as follows： orthorhombic system, space group P212121 with a = 13.8287（7）, b = 14.0715（7）, c = 25.7403（12） A^°, V = 5008.8（4） A^°3, Mr = 1333.08, Z = 4, F（000） = 2644, Dc = 1.768 g/cm^3, μ（MoKα） = 3.189 mm^-1, the final R = 0.0351 and wR = 0.0814 （I 〉 2σ（I））. Compound 1 displays an 8-connected bcu topology 3D framework and hydrogen-bonding interactions stabilize the solid-state structure. The vibrational circular dichroism （VCD） spectrum and second-order nonlinear optical effect of compound 1 have been studied in the solid state.

Synthesis, Structure, and the Second-order Nonlinear Optical Properties of a Borate-carboxylic Acid Compound: KB[L-（-）-C4H4O5]2·H2O

A new organic-inorganic hybrid noncentrosymmetric potassium bis(malic acid)-borates KB(L-(-)-C4H4O5)2·H2O was synthesized by solution method. It was characterized by elemental analysis, FT-IR, TGA and single-crystal X-ray crystallography. It crystallizes in the monoclinic space group P21/c with a = 5.546(6), b = 11.985(13), c = 9.952(11) ?, β = 97.522(17)°, V = 655.8(13) ?3, Z = 2, Dc = 1.682 g/cm3, μ(MoKa) = 0.46 mm–1 and F(000) = 340. 5009 reflections were measured and 2893 independent reflections(Rint = 0.051) were used for further refinement. Single-crystal X-ray diffraction reveals that the complex exhibits a threedimensional pseudo tunnel structure consisting of fundamental building block [B(L-(-)-C4H4O5)2]– anions. The small cavities are occupied by the H2O molecules, which stabilize the whole structure by O–H×××O hydrogen bonds. The complex exhibits nonlinear optical effect as high as 1.5 times that of KDP standard.

Nonlinear Optical Susceptibility and Refractive Index of Two Polyaniline Families

By use of the Keldysh non-equilibrium Green’s-function methods, the third harmonic susceptibilities of two polyaniline families, PANI-HCl and PANI-H 3PO 4, are calculated [ x (3) ( ω )≈10 -12 esu]. It was found that the third harmonic susceptibility of polyaniline strongly depends on the delocalization of the electrons. The refractive indices n ( λ =589 nm) of PANI-HCl and PANI-H 3PO 4 are calculated by use of three common methods (the Lorentz-Lorentz theoretical model, the Gladstone-Dale group contribution and the Vogel group correlation) based on group contributions to molar refraction. The calculated n values are varied from 1.31 to 1.42 for PANI-HCl and 1.36 to 1.45 for PANI-H 3PO 4.

Effect of Substituting Group on the Calculated Nonlinear Second－Order Optical Susceptibilities of Substituted Thiophene Derivatives with Quinoidlike Conformation

alculations of the nonlinear second-order optical susceptlbilities(β_(ijk))for sub- stituted tl1iophene derivative;with quinoidlike conformation are reported.These systetems possess small dipole moment;and large differences between dipole mo- ments of ground and first-excited states.Geometry optimizations of the molecules investigated were carried out using AM 1 method.The calculations were performed using INDO/CI method comboned with a sum-over-states expression for β_(jik). The calculated results sbw that the second-order susceptibility is a function of the na- ture and location of substituents and is larger for disubstituted molecules than monosubstituted molecules. Bipolymeric thiophenemetmne with NH_2/NO_2 groups was calctilated to have a β_μof 79. 920 × 10￣(-30) esu. It was found that the NH_2 and NO_2 groups in above disubstituted molecules are pull-pull groups in ground states,but are usual push-pull groups in the first excited states.

Fluorine-Mediated Benzothiadiazole Derivatives for Second-Order Nonlinear Optics

With increasing research interests in the field of light-matter interactions,various methods have been developed for regulating nonlinear optical(NLO)materials.However,the design and synthesis of organic molecular materials for second-order nonlinear optics remain a great challenge because of the strict requirement of the materials to possess a noncentrosymmetric structure.In this work,two benzothiadiazole(BTD)derivatives referred to as BTD-H and BTD-F were synthesized,and their NLO properties in the crystalline states were studied.It was found that introducing fluorine into the BTD backbone effectively tuned the crystal packing styles of BTD derivatives to a noncentrosymmetric system for effective second-order NLO responses.Such a strategy to induce the noncentrosymmetric structure by introducing the fluorine atoms and halogen interactions may provide guidance for future engineering of organic NLO molecular materials.

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.

Nonlinear optical properties of Au/PVP composite thin films

Colloidal Au and poly（vinylpyrrolidone） （PVP） composite thin films are fabricated by spin-coating method. Linear optical absorption measurements of the Au/PVP composite films indicate an absorption peak around 530 nm due to the surface plasmon resonance of gold nanoparticles. Nonlinear optical properties are studied using standard Z-scan technique, and experimental results show large optical nonlinearities of the Au/PVP composite films. A large value of χ^（3）/α up to 0.56× 10-^10esu·cm is obtained, which is comparable to the best values reported in metal/oxlde composite films.

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.

LENGTH DEPENDENCE OF THE NONLINEAR OPTICAL SECOND-ORDER SUSCEPTIBILITY ON CONJUGATED ORGANIC MOLECULES

It is known that organic conjugated molecules with delocalized π-electron systems exhibit large nonlinear optical responses. The conjugated length is an important factor contributing to the nonlinear optical susceptibility.

Influence of Kerr Effect on Second-Order Nonlinearity Induced Transparency

We theoretically study the effect of Kerr effect on the second-order nonlinearity induced transparency in a double-resonant optical cavity system.We show that in the presence of the Kerr effect,as the strength of the Kerr effect increases,the absorption curve exhibits an asymmetric-symmetric-asymmetric transition,and the zero absorption point shifts with the increase of the Kerr effect.Furthermore,by changing the strength of the Kerr effect,we can control the width of the transparent window,and the position of the zero-absorption point and meanwhile change the left and right width of the absorption peak.The asymmetry absorption curve can be employed to improve the quality factor of the cavity when the frequency detuning is tuned to be around the right peak.The simple dependence of the zeroabsorption point on the strength of Kerr effect suggests that the strength of Kerr effect can be measured by measuring the position of the zero-absorption point in a possible application.

AN EPOXY/(METHYL METHACRYLATE)INTERPENETRATING POLYMER NETWORK FOR NONLINEAR OPTICS

An interpenetrating polymer networks (IPN) consisting of an epoxy-based polymer network and a polymethyl methacrylate network were synthesized and characterized. The IPN showed only one T-g, and hence a homogeneous-phase morphology was suggested. The second-order nonlinear optical coefficient (d(33)) of the IPN was measured to be 1.72 X 10(-7) esu. The study of NLO temporal stability at room temperature and elevated temperature (100 degrees C) indicated that the IPN exhibits a high stability in the dipole orientation due to the permanent entanglements of two component networks in the IPN system. Long-term stability of second harmonic coefficients was observed at room temperature for more than 1000 h.

Synthesis and study the influence of yttrium doping on band structure,optical,non-linear optical and dielectric results for Ca_(12)Al_(14)O_(33) (C12A7) single crystals grown using traveling-solvent floating zone (TSFZ) method

Ca_(12)Al_(14)O_(33)(C12A7)and Y_(0.02)Ca_(11.98)Al_(14)O_(33)(Y-C12A7)single crystals were grown by using the traveling-solvent floating zone(TSFZ)method.The temperature was increased to avoid the bubbles and cracks which may be formed during the preparation of the ingot material.We have started with the flux higher than the normal to avoid the bubbles and make good treatment for the solid-liquid interface.The structures of both Ca_(12)Al_(14)O_(33)(C12A7)and Y_(0.02)Ca_(11.98)Al_(14)O_(33)(Y-C12A7)were studied by using x-ray diffraction(XRD).Optical properties for C12A7 and Y-C12A7 single crystals have been studied in order to determine the optical parameters such as optical energy gap(Eg),refractive index n,oscillating energy(Eo),dispersion energy(Ed),volume energy loss function(VELF),and surface energy loss function(SELF).Finally,a new result for these samples is that the third-order nonlinear optical susceptibility(χ(3))was determined.The results have been discussed with effect of Y-doping on the C12A7 single crystals for optical and industrial applications.

The Design of Second-order Nonlinear Optical Dendrimers:From"Branch Only"to"Root Containing"

Dendrimers are considered as a promising family of organic second-order nonlinear optical （NLO） polymers because of their well-defined structures, easily modified peripheral functional groups, interior branches and central cores. In order to obtain NLO materials with high performance, dendrimer structures have been optimized in the past years, such as the ＂branch only＂ and the ＂root containing＂ type dendrimers. This feature article highlights the achievements in exploring the rational design of dendrimers, partially marked by their macroscopic NLO performance.

Laser molecular-beam epitaxy and second-order optical nonlinearity of BaTiO_3/SrTiO_3 superlattices

A series of c-axis oriented BaTiO3/SrTiO3 superlattices with the atomic-scale precision were epitaxially grown on single-crystal SrTiO3(100) substrates using laser molecular-beam epitaxy (LMBE). A periodic modulation of the intensity of reflection high-energy electron diffraction (RHEED) in BaTiO3 and SrTiO3 layers was observed and attributed to the lattice-misfit-induced periodic variation of the terrace density in film surface. The relationship between the second-order nonlinear optical sus-ceptibilities and the superlattice structure was systematically studied. The experimental and theoretical fitting results indicate that the second-order nonlinear optical susceptibilities of BaTiO3/SrTiO3 superlattices were greatly enhanced with the maximum value being more than one order of magnitude larger than that of bulk BaTiO3 crystal. The mechanism of the enhancement of the second-order optical non-linearity was discussed by taking into account the stress-induced lattice distortion and polarization

Dendronized Polymers with High FTC-chromophore Loading Density:Large Second-order Nonlinear Optical Effects, Good Temporal and Thermal Stability

In this study,two new dendronized nonlinear optical(NLO)polymers were synthesized with high FTC chromophore loading density by introduction of high generation chromophore dendrons on the side chains.Due to their suitable molecular weights,both of them possessed good solubility in common solvents.They also inherited the advantages of dendrimers(large NLO coefficient),especially for PG2 whose NLO coefficient d33 value was as high as 282 pm·V^–1.Also,PG2 had a good temporal stability with 80%of its maximum value being retained at the temperature as high as 129℃.

Theoretical Studies on Electronic Spectra and Second-order Nonlinear Optical Properties of Glucosyl Substituted Barbituric Acid Derivatives

AMI semi-empirical method was used to optimize the barbituric acid derivatives substituted with glucosyl B1-5 （series B）, and the thiobarbituric acid derivatives substituted with glucosyl T1-5 （series T）. Based on the optimized structures, INDO/CI method was adopted to calculate the electronic spectra. Meanwhile, the second-order nonlinear optical （NLO） coefficients βμ were calculated with the sum-over-state （SOS） formula. The results show that when the number of glucosyl units was increased, ｜βμ｜ values of the barbituric and thiobarbituric acid derivatives were both enhanced, especially for thiobarbituric acid derivatives. It indicates that non-conjugated substituted group could also improve NLO properties of materials when the number of repeated units was increased. Additionally, the absorption bands appearing in UV area are consistent with the proper change of the number of glucosyl units, and consequently it can be concluded that the high transparencies of all systems were scarcely varied.

DFT Studies on Second-order Nonlinear Optical Response of Ir(C∧N)2(pic)Complexes

Density flmctional theory(DFT)was employed to calculate the geometrical structures,UV-Vis absorption spectra and second-order nonlinear optical(NLO)properties of a family of iridium(Ⅲ)complexes,which possess of different cyclometallated ligands(C∧N)and ancillary ligands[pyridme-2-carboxylate(pic)].It was found that the mo-dification of the LUMO energy levels was achieved by changing pic ligands and the energy gaps between the HOMO and LUMO were notably increased or decreased.In addition,the degree of conjugation was significantly changed with the substituent groups varied,which led to that the first hyperpolarizabilityβcould be effectively modulated.Through the analysis of time-dependent DFT(TD-DFT)results,we predicted that these studied complexes withπ→π^*charge transfer was beneficial to the large second-order NLO properties.Therefore,we hope that these studied iridium(III)complexes can be considered as versatile second-order NLO materials.

Middle-infrared Second-order Nonlinear Optical Chalcogenides and Halides Containing Multiple Anions

The second-order nonlinear optical(NLO)materials play an important role in the application and development of laser techniques.For various candidates,those in the middle infrared(MIR)region are far from the market’s requirement.Therefore,it is necessary to explore new ones with better performance.For their exploration,the inclusion of multiple anions in one structure has been proved to be a successful strategy.The NLO property contains several aspects,and different anions may contribute to different aspects.Therefore,the multiple anions’combination may give an opportunity to obtain NLO materials with desirable properties.Here,we make a short but clear summary on the MIR NLO-active chalcogenides and halides containing multiple anions,as most of them exhibit nice NLO performances.

Theoretical study on second-order nonlinear optical properties of unsymmetric bis (phenylethynyl) benzene series derivatives

On the basis of ZINDO methods, according to the sum-overstates (SOS) expression, the program for the calculation of the second-order nonlinear optical susceptibilities βijk and βμ of molecules was devised, and the structures and nonlinear optical properties of unsymmetric bis(phenylethynyl) benzene series derivatives were studied. The influence of the molecular conjugated chain lengths, the donor and the acceptor on βμ was examined.