A study of the structural phase transition in strontium titanate single crystal by coherent and incoherent second optical harmonic generation

The surface phase transition in a SrTiO₃ crystal was studied by second optical harmonic generation. Nonlinear optical response singularities were observed at temperature T*=145 K, which was 40 K higher than the T_c structural phase transition temperature in the crystal volume. Nonlinear critical opalescence in the crystal volume caused by the presence of point defects was studied. The second harmonic field and the intensity of critical opalescence were calculated based on the phenomenological model of nonlinear optical processes with the use of the Landau theory of phase transitions.     

Second-harmonic conversion of neodymium glass laser radiation with controlled spatial coherence

The experimental results on the second optical harmonic conversion of neodymium glass laser radiation with controlled spatial coherence in a nonlinear KDP crystal are presented. The conversion efficiency is studied depending on the radiation power density on the crystal and the crystal rotation angle in the principal optical plane with respect to the radiation propagation direction. The experiments were performed in the radiation power density range I = 0.2–3 GW/cm² for the number of cavity transverse modes N = 100–1000, radiation divergence 2ч = 0.5–3.5 mrad, spectrum width of 26 Å, and pulse duration of 2.5 ns.     

Synthesis,characterization and third-order nonlinear optical properties of polydiacetylene nanostructures,silver nanoparticles and polydiacetylene–silver nanocomposites

We have synthesized, characterized and studied the third-order nonlinear optical properties of two different nanostructures of polydiacetylene (PDA), PDA nanocrystals and PDA nanovesicles, along with silver nanoparticles-decorated PDA nanovesicles. The second molecular hyperpolarizability γ(?ω; ω, ?ω, ω) of the samples has been investigated by antiresonant ring interferometric nonlinear spectroscopic (ARINS) technique using femtosecond mode-locked Ti:sapphire laser in the spectral range of 720–820 nm. The observed spectral dispersion of γ has been explained in the framework of three-essential states model and a correlation between the electronic structure and optical nonlinearity of the samples has been established. The energy of two-photon state, transition dipole moments and linewidth of the transitions have been estimated. We have observed that the nonlinear optical properties of PDA nanocrystals and nanovesicles are different because of the influence of chain coupling effects facilitated by the chain packing geometry of the monomers. On the other hand, our investigation reveals that the spectral dispersion characteristic of γ for silver nanoparticles-coated PDA nanovesicles is qualitatively similar to that observed for the uncoated PDA nanovesicles but bears no resemblance to that observed in silver nanoparticles. The presence of silver nanoparticles increases the γ values of the coated nanovesicles slightly as compared to that of the uncoated nanovesicles, suggesting a definite but weak coupling between the free electrons of the metal nanoparticles and π electrons of the polymer in the composite system. Our comparative studies show that the arrangement of polymer chains in polydiacetylene nanocrystals is more favourable for higher nonlinearity.     

Thiourea-doped ammonium dihydrogen phosphate: A single crystal neutron diffraction investigation

Thiourea-doped ammonium dihydrogen phosphate (TADP) exhibits nonlinear optical property and the second harmonic generation efficiency of these crystals is three times that of pure ammonium dihydrogen phosphate (ADP) crystal. In this context, the study of structural distortion in the thiourea-doped ADP crystal is significant, hence single neutron diffraction investigations were undertaken. The final R-factors are: R[F ² > 2σ(F ²)] = 0.11, Goodness of fit(S) = 1.15. Though the dopant could not be located from the difference Fourier map, the cell parameters (a = b = 7.531(3) A, c = 7.544(5) Å) were found to be significantly greater than that of pure ADP at RT (a = b = 7.502(1) Å, c = 7.546(1) Å). This indicates that the dopant concentration in the crystals is small but enough to bring changes in the overall average structure.     

Study of third-and fifth-order nonlinear optical processes in thin C<Subscript>60</Subscript> films

The nonlinear refraction in thin films of fullerene C₆₀ (100 nm) is studied by the Z-and RZ-scan methods using the second harmonic of a picosecond Nd:YAG laser (λ = 532 nm, τ = 55 ps). The combined effect of n₂ (self-focusing of laser radiation) and n₄ (self-defocusing) is analyzed. Mechanisms responsible for the nonlinear refraction in films are discussed.     

DC-induced generation of the reflected second harmonic in silicon

DC-induced generation of the reflected second harmonic is experimentally observed on the surface of a centrosymmetric silicon single crystal. A direct current with a surface density of j _max ～ 10³ A/cm² violates the symmetry of the electron distribution function and induces the optical second harmonic with an intensity corresponding to the dipole quadratic susceptibility χ^(2)d (j _max) ～ 3 × 10^?15 m/V.     

Synthesis,growth and characterization of L-proline dimercuricchloride single crystals for frequency conversion applications

A semi-organic nonlinear optical L-proline dimercuricchloride (LPDMC) material has been synthesized. LPDMC single crystals were grown from aqueous solution by a slow cooling method. Good quality single crystals of size 19×6×3 mm³ have been grown over a period of 3 weeks. The grown crystals have been subjected to single crystal X-ray diffraction analysis to determine the cell parameters. The title compound crystallizes in the triclinic system with a noncentrosymmetric space group P1 and with unit-cell parameters a=7.2742(4) Å, b=9.4472(5) Å, c=10.4767(6) Å, α=108.621(3)^°, β=107.260(2)^°, γ=97.353(2)^° and volume=631.51(6) Å³. Optical and dielectric properties of the crystals have been studied. The thermal stability of the crystals was determined by thermogravimetric analysis/differential thermal analysis. The second harmonic generation efficiency of the crystals was obtained by the classical powder technique using a Nd:YAG laser and it is found to be 2.5 times that of potassium dihydrogen phosphate.     

CARS study of deuterium clusters stabilized in solid helium

Solid deuterium clusters that for the first time have been isolated in a matrix of solid helium have been investigated at T=1.3 K and P=3 MPa by the coherent anti-Stokes Raman spectroscopy (CARS) technique. The vibronic Q₁((J=0) and Q₁(J=1) line intensity, shape, and positions have been studied as functions of ortho and para content in the solid, as well as of the size of clusters. The strong effect of Raman scattering cross-section sensitivity to the molecular environment nuclear spin state has been found in CARS: the ratio of probabilities for the scattering by para(J=1) and ortho(J=0) deuterium, which is equal to 1 in a gas, is as high as 10000 in nearly pure ortho deuterium, whereas it is about 50 in spontaneous Raman scattering. This effect has been shown to occur starting from a cluster size corresponding to the onset of the phonon band.     

High-frequency nonlinear response of thin superconducting films with a mixed <Emphasis Type="Italic">d</Emphasis> and <Emphasis Type="Italic">s</Emphasis> symmetry of the order parameter

Third-harmonic generation during reflection of electromagnetic radiation from a thin superconducting film with a mixed d-and s-order parameter is studied theoretically. The dependence of the third harmonic intensity on the temperature and amplitude of an incident wave is calculated in the framework of the Ginzburg-Landau theory for superconductors with a two-component order parameter, and its behavior in the vicinity of transitions between phases with different symmetries is analyzed. It is shown, in particular, that the third harmonic intensity in the vicinity of the temperature corresponding to the d ? d + s phase transition substantially increases and is a nonanalytic function of the amplitude of the incident wave, while no singularity in the nonlinear response is observed for the d ? d + is transition. The linear reflection coefficient is found to be virtually insensitive to these phase transitions.     

Harmonic analysis of coefficients of free energy decomposition in the polarization of a Rb<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal

Landau–Devonshire decomposition coefficients W_C in a series with respect to P_C are determined via harmonic analysis of experimental free energy coordinates W_C of a Rb₂ZnCl₄ crystal, depending on its polarization P_C. The number of terms needed in W_C decomposition is determined for quantitative evaluation of the measured data.     

Phase transition in a KPb<Subscript>2</Subscript>Br<Subscript>5</Subscript> crystal

Crystals of the KPb₂Br₅compound are investigated using polarized light microscopy and calorimetry. The birefringence and the angle of rotation of the optical indicatrix are measured in the temperature range 270–620 K. It is found that the KPb₂Br₅ crystal undergoes a first-order ferroelastic phase transition at temperatures T_0↑ = 519.5 K and T_0↓ = 518.5 K with a change in the enthalpy ΔH = 1300 ± 200 J/mol. This transition is accompanied by both twinning and the symmetry change mmm ? P2₁/c. It is revealed that the angle of rotation of the optical indicatrix exhibits an unusual behavior under variations in the temperature due to a strong temperature dependence of the birefringence.     

Electronic and structural transitions in NdFeO<Subscript>3</Subscript> orthoferrite under high pressures

The effect of high pressure up to 65 GPa on the crystal structure and optical absorption spectra of NdFeO₃ orthoferrite single crystals is studied in diamond anvil cells. At P～37.5 GPa, an electronic transition at which the optical absorption edge jumps from ～2.2 to ～0.75 eV is observed. The equation of state V(P) is studied on the basis of the X-ray diffraction data obtained under pressure. This study reveals a first-order structural phase transition at P～37 GPa with a jump of ～4% in the unit cell volume. It is shown that the phase transition observed in rare-earth orthoferrites at 30–40 GPa is a transition of the insulator-to-semiconductor type.     

Substituent Dependent Optical Properties of <Emphasis Type="Italic">p</Emphasis>-phenyl Substituted ethenyl-<Emphasis Type="Italic">E</Emphasis>-thiophenes

Various electron donor and acceptor substituted (NO₂, CN, Cl, H, OCH₃, NH₂) p-phenyl ethenyl-E- thiophenes (1–6) were synthesized and substituent dependent optical properties (dipole moment, transition dipole moment, oscillator strength, optical band gap, hyperpolarizability) were studied using Solvatochromism and Density functional theory. It is shown that thiophene acts as a weak electron donor in presence of an electron withdrawing p-phenyl substituent (NO₂, CN, Cl), whereas thiophene acts as a weak electron acceptor in presence of an electron donating p-phenyl substituent (OCH₃, NH₂). In comparison to ethenyl thiophene 4, the HOMO-LUMO energy band gap is decreased upon increasing the electron donating or electron withdrawing capacity of p-phenyl substituent. From the excited state dipole moment calculation, it is shown that the excited state is highly dipolar for nitro and amino compounds 1 and 6, whereas compounds 2–5 show a non-polar excited state. As compared to the ethenyl thiophene 4, the first hyperpolarizability (β) increases upon substitution either with a strong electron withdrawing or strong electron donating p-phenyl substituent. A large β value is found for p-nitro phenyl ethenyl-E-thiophene and p-amino phenyl ethenyl-E- thiophene. Overall, these studies provide useful information in understanding the optical properties of phenyl and heterocyclic based ethenyl systems.     

Enhancement of resonant bleaching of <Emphasis Type="Italic">J</Emphasis>-aggregates upon lengthening of an exciting radiation

Thin films of J-aggregates of a new amphiphilic thiacarbocyanine dye of the benthiazole series are prepared and the nonlinear optical response of molecular J-aggregates is studied for femto-and nanosecond exciting radiation pulses. It is found that the nonlinear optical response of J-aggregates exhibits substantial enhancement upon an increase in the pulse duration, which cannot be described by the saturation effect in the model of a two-level system. This effect is considered using a three-level model taking into account the formation of self-trapped exciton states in molecular J-aggregates.     

Theoretical prediction of a surface-induced spin-reorientation phase transition in BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanocrystals

The equation of the magnetization of a hexagonal crystal is derived for the first time for an arbitrary orientation of the external magnetic field relative to the crystallographic c axis. In order to clarify the magnetization mechanism for a real ensemble of small particles in the framework of the given problem, surface anisotropy (which is significant for nanosize objects) was taken into account along with crystalline magnetic anisotropy and anisotropy in the particle shape. Model computer experiments prove that the magnetization curves for nanocrystals oriented in a polar angle range of 65–90° exhibit an anomaly in the form of a jump, indicating a first-order spin-reorientation phase transition. This explains a larger steepness of the experimental curve reconstructed taking into account the interaction between particles as compared to the theoretical dependence obtained by Stoner and Wohlfarth [IEEE Trans. Magn. MAG 27 (4), 3469 (1991)]. An analysis of variation of the characteristic anisotropy surface and its cross section with increasing ratio |K₂|/K₁ of the crystalline magnetic anisotropy constants upon a transition from a macroscopic to a nanoscopic crystal shows that surface anisotropy leads to a change in the magnetic structure. As a result, an additional easy magnetization direction emerges in the basal plane apart from the easiest magnetization direction (along the c axis). The direction of hard magnetization emerges from the basal plane, the angle of its orientation relative to the c axis being a function of the ratio | K₂|/K₁.     

Dependence of the surface energy on the size and shape of a nanocrystal

An expression is derived for the surface energy σ as a function of the size and shape of a nanocrystal. It is shown that the wider the deviation of the shape parameter f from unity, the more pronounced the decrease in the surface energy σ with a decrease in the number N of atoms in the nanocrystal. The dependences of the average coordination number, the surface energy, and the melting temperature on the number N exhibit an oscillatory behavior with maxima at points corresponding to numbers of atoms forming a defect-free cube. The surface energy decreases with an increase in the temperature T. It is found that the smaller the nanocrystal size or the greater the deviation of the nanocrystal shape from the thermodynamically most stable shape (a cube), the larger the quantity-(dσ/dT). It is established that the nanocrystal undergoes melting when the surface energy decreases to a value at which it becomes independent of the nanocrystal size and shape. The conditions providing fragmentation and dendritization of the crystal are discussed. It is demonstrated that, at N>1000, the dependence σ(N) coincides, to a high accuracy, with the dependence of the surface tension of the nanocrystal on N. The inference is made that bimorphism is characteristic of nanocrystals. This implies that nanocrystals can have platelike and rodlike shapes with equal probability.     

Second and third-order nonlinear optical behavior of natural pigment: chlorophyll and crocin

To provide an insight into the microscopic second and third-order nonlinear optical (NLO) behavior of chlorophyll a and crocin, we have computed the electric dipole moments (μ), dispersion-free first hyperpolarizabilities (β), frequency-dependent first and second (γ) hyperpolarizabilities at 1064 nm wavelength area using time-dependent Hartree-Fock (TDHF) method. According to ab-initio calculation results, the examined compounds exhibit first and second hyperpolarizabilities with non-zero values, implying second and third-order NLO phenomena.     

New experimental criterion of the Berezinskii-Kosterlitz-Thouless transition

Based on the experimental study of YBa₂Cu₃O_7?x single crystal nonlinearity near T _c , a new criterion for observing the Berezinskii-Kosterlitz-Thouless (BKT) transition in cuprate HTSC compounds was proposed. The criterion consists in the existence of the maximum in the dependence of the voltage of the second harmonic of the sample response signal excited by alternating current on the direct bias current. It was shown that the position of the second harmonic maximum is independent of temperatures near T _c , which is consistent with the BKT transition independence of the measuring current.     

Spin-lattice and spin-spin relaxation times of 2,4,6-tri-<Emphasis Type="Italic">tert</Emphasis>-butyl phenoxyl and 2,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-4-methyl phenoxyl in diamagnetic crystals: Relaxation mechanism and influence of molecular motions

The spin-lattice and phase-memory times were determined for 2,4,6-tri-tert-butyl phenoxyl and 2,6-di-tert-butyl-4-methyl phenoxyl dispersed in a diamagnetic matrix by use of primary and stimulated echoes. The temperature variations from room temperature and lower to liquid helium indicated interesting characteristics, albeit there were no echo signals between 150 and 100 K. It may be concluded that the relaxation times vary depending on the motional fluctuation of substituted molecular groups on the π-conjugated framework. In particular, the methyl rotational motion of thetert-butyl groups at theortho-positions or thepara-position is a dominant contribution, andtert-butyl rotation itself and additional methyl rotation at thepara-position are also responsible for the shortening, especially in the phase-memory times. The shortening of the relaxation times when approaching liquid helium temperature is probably due to the quantum mechanical tunneling effect of the methyl substituents.     

Line shape of <Superscript>57</Superscript>Co sources exhibiting self absorption

The effect of selfabsorption in Mössbauer sources is studied in detail. Spectra were measured using an old ⁵⁷ C o/R h source of 74M B q activity with an original activity of ca. 3.7G B q and a 0.15G B q ⁵⁷ C o/α ? F e source magnetized by an in-plane magnetic field of 0.2 T. The ⁵⁷ C o/α ? F e source of a thickness of 25 μ was used both from the active and the inactive side giving cause to very different selfabsorption effects. The absorber was a single crystal of ferrous ammonium sulphate hexahydrate (FAS). Its absorption properties were taken over from a detailed study (Bull et al., Hyperfine Interact. 94(1–3), 1; Spiering et al. 2). FAS (space group P21/c) crystallizes as flat plates containing the (\(\overline {2}\)01) plane. The γ-direction was orthogonal to the crystal plate. The ⁵⁷ C o atoms of the ⁵⁷ C o/R h source were assumed to be homogeneously distributed over a 6μ thick Rh foil and to follow a one dimensional diffusion profile in the 25 μ Fe-foil. The diffusion length was fitted to 10 μ. The theory follows the Blume-Kistner equations for forward scattering (Blume and Kistner, Phys. Rev. 171, 417, 3) by integrating over the source sampled up to 128 layers.