New Additions to Nonconjugated Conductive Polymers; Nonlinear Optical Effects

Recently, new additions to nonconjugated conductive polymers have been made that include: poly(β-pinene), poly(ethylenepyrrolediyl) derivative and polynorbornene. These polymers have different double-bond number fractions per repeat compared to previously reported nonconjugated conductive polymers. Upon doping with electron acceptor (e.g. iodine) the conductivities increase more than ten orders of magnitude to levels consistent with their double-bond number fractions. Radical cations that are formed upon doping have dimensions less than a nanometer leading to unexpectedly large nonlinear optical effects. The measured Kerr coefficient of doped polyisoprene is ～1.6 × 10^-10 m/V² at 633 nm. For doped poly(β-pinene) the Kerr coefficient is ～1.2 × 10^-10 m/V² and for poly(ethylenepyrrolediyl) derivative it is ～1.2 × 10^-9m/V². Exceptionally large two-photon absorption coefficient (～2.6 cm/MW at 810 nm) has been measured for doped poly(β-pinene). The mechanism of the nonlinear optical effect has been explained using a model of subnanometer size metallic quantum dots. These novel materials with wide transparency are expected to have significant applications in photonics.     

Phase diagram and electro-optical Kerr effect of nematic mixtures containingtolane and biphenyl cores

An experimental phase diagram for two types of nematic liquid crystals and their binary mixtures was established by polarised optical microscopy and differential scanning calorimetry methods. The mixtures comprised a tolane-base liquid crystal, 4-heptyl-3-fluoro-4-isothiocyanatotolane (7TOLF), and a biphenyl-base nematogen, 4-heptyl-3-fluoro-4-isothiocyanatobiphenyl (7BF). The static Kerr effect and third-order non-linearity were investigated for 7TOLF and 7BF and their nematic mixtures within the isotropic phase. Both the compounds have a positive and large Kerr constant. The second-order phase-transition temperatures, T?, were determined for these mixtures. The linear dependence of (T - T?)^??1 on the Kerr constant is found to be in good agreement with the predications of the Landau–de Gennes model. The third-order non-linear susceptibility,χ⁽³⁾, values were determined for these mixtures.     

The magnitude and temperature dependence of the Kerr constant in liquid crystal blue phases and the dark conglomerate phase

A new method of evaluating the Kerr constant in liquid crystals (LCs) is used to determine the temperature dependence of the Kerr effect in blue phases I and II (BPI and BPII) and to investigate the Kerr constant of the isotropic dark conglomerate (DC) phase. This method employs relatively small driving voltages and a vertical field switching (VFS) device geometry. An unusually large Kerr constant, K, is determined in the BPs of a non-polymer-stabilised material, ～3×10^?9 mV^?2 (BPI). The large value of K is attributed to significant pre-transitional values of the dielectric anisotropy and birefringence. K follows an inverse dependence on temperature and we consequently suggest that BPI demonstrates properties best suited to electro-optic devices. The new methodology has the advantage of revealing the dispersion of K in a single measurement. It is also possible to deconvolute the influence of the Kerr effect from measurements of electrostriction of the BP lattice. Finally, the Kerr effect has been measured for the first time in the DC phase of an oxadiazole bent-core liquid crystalline material, and is found to take rather low values, ～1×10^?11 mV^?2, which can be understood in the context of the physical properties of the material.     

Optical Kerr effect in carbon diselenide

We have measured the optical Kerr susceptibility of liquid carbon diselenide and find its value to be (74 ± 11) × 10^?14 csu, with pump and probe wavelengths of 619 and 579 nm, respectively. This value is approximately three times the Kerr susceptibility of carbon disulfide, and is the largest value reported for a simple liquid. A strong dispersion in Kerr susceptibility is observed as the probe frequency is tuned toward the blue, and is likely due to two-photon near-resonant enhancement from the ¹B₂ state. We also report the visible and ultraviolet absorption spectra and linear refractive index measurements of liquid CSe₂.     

Time resolved fluorescence of anthracene in mixed crystals at 2K

An optical Kerr shuttered spectrograph has been used to time resolve the spontaneous fluorescence of aromatic mixed crystal systems at low temperature with moderate resolution. Transient effects on the fluorescence of anthracene in naphthalene excited with 614 cm^?1 vibrational excess energy in ¹B_2u have been observed that may signal measurable vibrational relaxation pathways. A model consistent with these observations is presented: it implicates a strong interaction between the intramolecular Franck—Condon and non-Franck—Condon modes in the relaxation process for specific excitation in the region of large excess lattice energy. Examination of the fluorescence for several aromatic systems integrated over the interval 0 to 30 ps following excitation high in the S₁ vibrational manifold failed to reveal evidence of non-Boltzmann vibrational distributions, although other largely unexplained effects have been observed.     

Femtosecond molecular motions and implications for electron solvation dynamics in liquids

Molecular motions at femtosecond times are observed experimentally, via nonlinear laser spectroscopy, as responses to the imposition of a sudden, intense laser field in the optical Kerr effect. The electronic, librational, collision-induced translational and reorientational diffusional motions identified through the nonlinear polarizability responses are linked to the probable responses of the disordered medium to an excess electron undergoing multiple scattering at times <10^-12s.     

Large optical Kerr effect in bulk GeSe2–In2Se3–CsI chalcohalide glasses

Third-order nonlinear optical properties of GeSe₂–In₂Se₃–CsI chalcogenide bulk glasses are studied by Standard pico-second (ps) time-resolved optical Kerr effect (OKE) technique. The obtained χ⁽³⁾ and n₂ at 1064 nm of the glass 72.25GeSe₂–23.75In₂Se₃–5CsI are as large as 10.07 × 10⁻¹² esu and 6.5 × 10⁻¹⁸ m²/W, respectively, more than twice that of As₂S₃ glass. The relationship between glass compositions and the third-order nonlinear optical responses was analyzed by Raman spectra in terms of structural evolution. It is suggested that the tetrahedral units ([GeSe₄] and [InSe₄]) play an important role in the ultrafast third-order nonlinear optical responses of these chalcohalide glasses.     

Electrooptical properties and structure of lanthanide 3-trifluoroacetylcamphorates

Kerr effect and optical activity data indicate that Pr³⁺, Dy³⁺,and Yb³⁺ 3-trifluoroacetylcamphorates in CCl₄ exist predominantly in one form with virtually octahedral orientation of the chelate rings.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 486–489, February, 1990.Deceased.     

Kerr constant of water from 280 to 350 K at 632.8 nm

The Kerr constant (B_T) of deionized liquid water was measured in the temperature range from 280 K to 350 K using 2 μs duration electric pulse fields up to 50 kV cm^?1. The value of B_T has been determined as 2.92 × 10^?14 mV^?2 at 298 K. Results indicate a steady decrease in the value of the Kerr constant with the rise of temperature.     

Electrical and Optical Properties of the Nitramine Group and Molecular Structure of Some N-Nitramines

The electrical and optical properties (dipole moment, electrooptical and optical Kerr constants, molecular polarizability anisotropy, polarizability tensor, molecular refraction) of N,N-dimethylnitramine as the simplest N-NO₂ derivative were studied by a set of experimental and theoretical methods with the aim to determine the components of the polarizability ellipsoid of the N-NO₂ group and develop a valence-optical scheme for calculating the optical and electrooptical parameters of N-NO₂ compounds. Conjugation of the p electrons of the imide nitrogen atom with the electrons of the nitro group results in deviation of the properties of N,N-dimethylnitramine from the additive values. Comparative evaluation of the parameters of the Csp³-NO₂, Csp²-NO₂, and N-NO₂ groups was made.     

The synthesis and structural study of five-coordinate triorganotin(IV) tropolonates and dibenzoylmethanates

The complexes [1,3-diphenyl-1,3-propanedionato]tricyclohexyltin(IV), (tropolonato)triphenyltin(IV), and (tropolonato)tricyclohexyltin(IV) have been prepared for the first time and have been found to be five-coordinate in the solid state. These and related five-coordinate complexes prepared previously have been studied by a variety of physical methods; ¹³C NMR, UV, IR, Raman, dipole moments and the Kerr effect. While all structures are demonstrably five-coordinate, and all chelates bidentate in the solid state, the geometries of two of the complexes in solution appear to vary somewhat from the expected fac or mer. There is evidence from the solution Kerr effect and ¹³C NMR that cyclohexyl derivatives may disproportionate.     

Dynamooptical and electrooptical properties of poly(methylphenylsiloxane) in solution and bulk

The dynamooptical, electrooptical, and hydrodynamic properties of a low-molecular-mass poly(methylphenylsiloxane) containing 33% phenyl radicals (with respect to the total amount of side groups) in dilute solutions and in bulk are studied. The size of macromolecules, as well as the molecular mass of the polymer, its shear optical coefficients Δn/Δτ = (0.29 ± 0.3) × 10^?10 (in decalin) and (0.43 ± 0.03) × 10^?10 cm s²/g (in bulk), and the specific Kerr constants K = (2.30 ± 0.02) × 10^?12 (in benzene), (2.23 ± 0.02) × 10^?12 (in decalin), and (2.24 ± 0.09) × 10^?12 cm⁵/[g (300 V)²] (in bulk), are estimated and compared with the corresponding characteristics of poly(dimethylsiloxane). The effect of solvents on the intramolecular mobility, optical anisotropy, and dipole structure of polymer macromolecules is considered.     

Femtosecond photoexcitation dynamics in polydiacetylene 4BCMU film

Femtosecond pulses were used to study photoexcitation dynamics in polydiacetylene 4BCMU film. Ultrafast photoinduced dichroism and optical Kerr gate responses were observed. These measurements allowed estimation of the diffusion constant (D ∼ 0.1 cm²/s), the nonlinear index of refraction (n₂ ∼ 10⁻⁸ esu), and third-order susceptibility (δχ⁽³⁾ ∼ 6 × 10⁻¹⁰ esu), in the film. We also found that the sign of the photoinduced transmission signal was dependent on the pump energy at the low energy absorption edge of the film. Possible explanations are proposed.     

Characterizing polymers with heterogeneous micro‐ and macrostructures

The potentially extreme heterogeneity of polymer micro‐ and macrostructures has been demonstrated and a means for characterizing them has been suggested. To ensure that all possible microstructures, such as diad stereosequences in vinyl homopolymers and monomer sequences in copolymers, including their locations along polymer chains, that is, all macrostructures, are represented, it became necessary to generate samples with huge quantities (many many tons) of constituent polymer chains. This suggested a practical need for distinguishing between polymer samples with chains that have homogeneous and heterogeneous populations of micro‐ and macrostructures. A combination of high resolution ¹³C‐nuclear magnetic resonance to determine the types and amounts of constituent short‐range microstructures, and dilute solution electrical birefringence or Kerr effect measurements to locate them along the polymer chains has been suggested, and may be able to achieve this distinction. This combination of techniques is required to reduce the innumerably large numbers of different possible polymer macrostructres whose Kerr constants would have to be calculated, for comparison to the observed values. The ability to determine polymer macrostructures is critical to the development of relevant, more meaningful, and therefore, improved structure–property relations for polymer materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 409–414     

Third- and second-order optical nonlinearity of Ge-Ga-S-PbI2 chalcohalide glasses

Two series of metal iodide doped chalcohalide glasses (100−2x)GeS₂·xGa₂S₃·xPbI₂ (0?x?20) and (100−x)(0.8GeS₂·0.2Ga₂S₃)·xPbI₂ (0?x?15) were prepared and characterized. The microstructure of these glasses has been studied by Raman scattering spectra. Utilizing femtosecond time-resolved optical Kerr effect (OKE) technique at the wavelength of 820 nm, a largest third-order nonlinearity χ⁽³⁾ of 2.07×10⁻¹³ esu was obtained for the 90GeS₂·5Ga₂S₃·5PbI₂ glass, and it decreases with the addition of PbI₂ in both two series. After thermally poled, second-harmonic generation (SHG) has been observed in these glasses according to Maker fringe method and a large second-order nonlinearity χ⁽²⁾ as well as 4 pm/V was obtained for the 70GeS₂·15Ga₂S₃·15PbI₂ glass. The variations of χ⁽²⁾ and χ⁽³⁾ on glass composition are ascribed to the evolution of micro-structural units in glass. These novel chalcohalide glasses would be expected to be the promising candidate materials for nonlinear optical devices.     

The second order hyperpolarizability of cis azobenzene isomer

The second order hyperpolarizability of cis azobenzene isomer (γ_c) was obtained by measuring the third harmonic generation (THG) variation of an azobenzene doped polymer film when the film was optically pumped to create a large amount of cis isomers via photoisomerization. A steady state theory was developed to treat the THG intensity variation by considering the optical pump induced redistribution and reorientation of azobenzene in the polymer film and the contribution of cis isomer to the THG signal. The ratio of γ of cis and trans molecule, (γ_c/γ_t), was found to be 0.51. After the γ_t was obtained from the time-resolved optical Kerr effect (OKE) measurement, γ_c was deduced to be 5.6 × 10⁻³³ esu. The result shows that the optical nonlinearity of cis isomer is clearly not negligible.     

Third-order Nonlinear Optical Properties of Octa-substituted Metal-free Phthalocyanine Thin Films

Third-order nonlinear optical susceptibility, χ⁽³⁾ of symmetrically octa-substituted metal-free phthalocyanine thin films measured by the third-harmonic generation technique are reported. The metal-free phthalocyanine has been found to show a χ⁽³⁾ (−3ω; ω,ω, ω) value as large as 7.73×10⁻¹² esu at 1.80 μm. The figure of merit, χ⁽³⁾/α, was estimated to be 4.17×10¹⁷ esu cm at 1.05 μm and 6.97×10¹⁶ esu cm at 1.65 μm. Both linear and third-order optical properties of liquid-crystalline metal-free phthalocyanines are discussed     

Kerr Effect of Xanthan/DTAB Aqueous Solutions

The Kerr effect of the Xanthan (charged polyelectrolyte; 113 ppm)/DTAB (surfactant) mixture in aqueous solution was studied. The static Kerr constant (B) and mean relaxation times (τ) values as a function of surfactant concentration (C_DTAB ) were determined. The observed birefringence (Δn) is not a linear function of the electric applied field (E ²). For small E values Δn grows with E ² and at a certain field value the birefringence tends to saturate. The addition of small quantities of DTAB lowers B values with respect to the Kerr constant of Xanthan (113 ppm) aqueous solution. The relaxation time of the mixtures is linearly dependent on the applied field and it decreases when DTAB concentration increases. The importance of the equivalent point is signalled. It is supposed that the initial rigidity of the polyelectrolite decreases because of the surfactant addition. Conductivity (σ) values as a function of surfactant concentration are presented.     

Investigation of third-order nonlinearity of an azo dye and its metal-substituted compounds

The real part of third-order optical nonlinearity of an azo dye (2-(2-thiazolylazo)-5-diethylaminophenol, TAEP) and those of its copper- and cobalt-substituted compounds are measured by using femtosecond optical heterodyne optical Kerr gate technique at the wavelength of 647 nm. All the values are found to be negative. Those of Cu- and Co-substituted compounds are found to be larger than that of the metal-free dye by two and three orders of magnitude, respectively. A negative γ_eff as large as 10⁻²⁹ esu is found in Co complex. We use a three-level model to characterize the nonlinear process, and suggest that π-electron delocalization in metal complex leads to an enhancement.     

Laser-induced Kerr constants for alkanoic acids at 532 and 1064 nm inducing wavelengths

The nanosecond optical Kerr constants of a series of alkanoic acids from formic acid to nonanoic acid have been measured at the two inducing wavelengths of 532 and 1064 nm. Results indicate that the values are of similar magnitude to a previous study of the 1-alkyne series and exhibit a similar behaviour of relatively invariant values amongst the higher members of the series. This effect is attributed to the dominant contribution of the carbonyl group to the observed optical Kerr constant.