Investigation of the nonlinear absorption and optical limiting properties of two [Q]2[Cu(C3S5)2] compounds

The nonlinear absorption properties of two organometallic compounds, [(C₂H₅)₄N]₂[Cu(C₃S₅)₂] (DCu1) and [(C₄H₉)₄N]₂[Cu(C₃S₅)₂] (DCu2), have been investigated using an open-aperture Z-scan technique at 1064 nm with 40 ps pulse width and at 1053 nm with 18 ns pulse width. The reverse saturable absorption (RSA) which was observed in both samples with nanosecond pulse excitation was much larger than that observed with picosecond pulse excitation. The nonlinear absorption properties were analyzed theoretically by a five-level model. Optical limiting based on RSA was performed and limiting thresholds were evaluated for both samples under three conditions. DCu1 exhibited the better limiting characteristics because of its stronger RSA response.     

Nonlinear optical properties of [（CH3）4N]Au（dmit）2 using Z-scan technique

The third-order optical nonlinearities of [（CH3）4N]Au（dmit）2 （dmit = 4,5-dithiolate-1,3-dithiole-2-thione） at 532 nm and 1064 nm are investigated using the Z-scan technique with pulses of picoseconds duration. The Z-scan spectra reveal a strong nonlinear absorption （reverse saturable absorption） and a negative nonlinear refraction at 532 nm. No nonlinear absorption is observed at 1064 nm. The molecular second-order hyperpolarizability γ for the [（CH3）4N]Au（dmit）2 molecule at 532nm is estimated to be as high as （2.1 ±0.1） × 10^-31 esu, which is nearly three times larger than that at 1064 nm. The mechanism responsible for the difference between the results is analysed. Nonlinear transmission measurements suggest that this material has potential applications in optical limiting.     

Investigation of optical nonlinearities in Pd(po)2 by Z-scan technique

With nanosecond scale at a 532 nm wavelength, we firstly measured the nonlinear optical absorption and refraction coefficients of Pd(po)₂ complex by using Z-scan technique, here Hpo=1-hydioxy-2-pyridone. We describe an empirical expression for the case when nonlinear refraction is accompanied by nonlinear absorption to separately evaluate the nonlinear refraction and the nonlinear absorption by performing straightforward measurements with the aperture removed. The nonlinear optical response of Pd(po)₂ was determined by the linear decreasing irradiance-dependence. The nonlinear absorption originates from the near resonant two-photon absorption while the mechanism of the nonlinear refraction is the near resonant two-photon absorption transition enhancement. The linear increasing dependences of the optical nonlinearities on the incident irradiance arise from the population redistribution due to the near resonant two-photon absorption.     

Z-scan measurement for the nonlinear absorption and the nonlinear refraction of poly1,4-diazophenylene-bridged-tris(8-hydroxy-quinoline) aluminum (PDPAlq3)

The nonlinear optical properties of the poly1,4-diazophenylene-bridged-tris(8-hydroxy-quinoline) aluminum (PDPAlq₃) solution were studied using single beam Z-scan technique with a continuous-wave Diode laser radiation at 657.2 nm with 10 Hz repetition rate. The results show that the solution of PDPAlq₃ exhibits large nonlinear refractive index (n₂ = −1.7642 × 10⁻¹² m²/W) and nonlinear absorption coefficient (β = 1.12 × 10⁻⁶ m/W). The negative sign of the nonlinear refractive index n₂ indicates that the material exhibits self-defocusing optical nonlinearity. The evaluation of the figure of merit (W = 1.8) shows that the solution of PDPAlq₃ is sufficient for application in all-optical switching technology. These results show that the solution of PDPAlq₃ have potential application in nonlinear optics.     

Electron paramagnetic resonance of gamma irradiated [(CH3)4N]InCl4 and [(CH3)4N]2CdCl4 single crystals

Gamma irradiated [(CH₃)₄N]InCl₄ and [(CH₃)₄N]₂CdCl₄ single crystals were investigated by electron paramagnetic resonance at ambient temperature, and it has been found that both compounds indicate the existence of (CH₃)₃N⁺ radicals. The g factors were found to be isotropic, and the hyperfine constant for H atoms was measured as 2.86 mT and is isotropic for this radical in these substances. The hyperfine coupling constant of the N nucleus with the hole in (CH₃)₃N⁺ in [(CH₃)₄N]InCl₄ was found to be anisotropic with the A_zz=2.92, A_yy=1.62 and A_xx=1.40 mT. From these, it has been revealed that the C_3v-axis of (CH₃)₃N⁺ radical performs rotational or jumping reorientational motions around a fixed axis, in addition to the rotations of protons in CH₃ groups and the rotational motions of CH₃ groups around the C_3v-axis of the radical. The g, and the hyperfine coupling factors of the N nucleus were isotropic in (CH₃)₃N⁺ in [(CH₃)₄N]₂CdCl₄. This indicates the motional behaviour of the radical in this compound is as in a liquid. This isotropic behaviour of the hyperfine coupling constants was found to be same until the attainable lowest temperature of 113 K in our laboratory.     

Third order nonlinear optical properties of potassium dichromate single crystals by Z-scan technique

Single crystal of potassium dichromate (KDC) has been grown from aqueous solution by slow evaporation technique. The lattice parameters of the grown crystal were determined by X-ray diffraction analysis. The optical absorption studies reveal that the crystal has UV cut-off wavelength around 240 nm. Thermo gravimetric and differential thermal (TGA/DTA) studies revealed that the crystal thermally stable up to 397.1 °C. The mechanical strength of the grown crystal was carried out by Vickers micro hardness test. The crystal perfection was confirmed by etching studies. Third order nonlinear optical studies was performed using by single beam Z-scan technique using continuous Nd:YAG laser. Closed aperture Z-scan studies reveal the negative nonlinearity in the crystals and open aperture Z-scan reveals the saturation absorption. Also various parameters such as nonlinear refractive index n₂, absorption co-efficient β and nonlinear optical susceptibility χ⁽³⁾ were calculated for the grown crystal.     

The possibility of observing a soliton mode in [(CH3)4N] [NiCl3] by neutron scattering experiments

The contribution of solitons, existing as bound states of spin excitations and lattice oscillation, to the dynamic structure factor in ferromagnetic chains of [(CH₃)₄N] [NiCl₃] is evaluated. At sufficiently low temperatures these low-energy soliton excitations determine the thermodynamic properties of the system and can be revealed by observing the quasielastic component in the neutron scattering spectrum.     

Dielectric dispersion in the incommensurate phases of [N(CH3)4]2CoCl4 and [N(CH3)4]2ZnCl4

The complex dielectric permittivity ?(ω) of [N(CH₃)₄]₂CoCl₄ and [N(CH₃)₄]₂ZnCl₄ along the a-axis was measured between 0.35 MHz and 100 MHz. It has been found that for both substances the relaxation frequencies are about 5 MHz at T_c. The dielectric relaxation of both substances could be described by a polydispersive process β = 0.74 in the vicinity of T_c. However, for the temperature region of (T?T_c) > 0.6 for [N(CH₃)₄]₂CoCl₄ the dielectric absorption seems to be rather monodispersive.     

Study of nonlinear absorption in GaAs/AlGaAs multiple quantum wells using the reflection Z-scan

The room-temperature third order nonlinearities in GaAs/AlGaAs multiple quantum wells have been studied using reflection Z-scan technique. Band-filling effect is considered to be the major nonlinear mechanism of the nonlinear absorption. A model to calculate the absorption coefficient of quantum wells in the nonlinear regime is presented.      

Low temperature far IR spectra of (CH34)N NiCl3, (CH3)4N NiBr3 and (CD3)4N NiBr3

The known phase transition in (CH₃)₄N NiCl₃, at 171 K, has been characterised by far IR spectroscopy. The transition is explained as due to a formation of weak labile C-H,…, Cl hydrogen bonds at low temperatures, restricting the “free” internal rotations of the methyl groups and perhaps at the same time ordering the orientations of the tetramethylammonium ions. No similar transition in (CH₃)₄N NiBr₃ was found.     

Thermoelectric power of TTF[Ni(dmit)2]2

The 1D organic salt TTF[Ni(dmit)₂]₂ becomes superconductor with T_c=1.6 K under an applied hydrostatic pressure of 7 kbar. Structural determinations in this system lead us to suspect that superconductivity (SC) coexists with a charge density wave (CDW) instability at low pressure. In order to better understand how SC emerge from a CDW and to revisit the pressure–temperature phase diagram of the TTF[Ni(dmit)₂]₂ we performed transport and thermoelectric power measurements under pressure.     

On the phase diagram of the [(CH3)4N]2ZnCl4−xBrx system

The [(CH₃)₄N]₂ZnCl_4?xBr_x system shows a complete miscibility with a common Pnma high temperature phase. The (x,T)-phase diagram (x given by [(CH₃)₄N]₂ZnCl_4?xBr_x) was determined by means of DSC- and X-ray measurements. In the vicinity of both end members an analogy to the (P,T)-phase diagrams of pure compounds is observed with an increasing x corresponding to an increase of pressure. In the intermediate part of the system other effects become important leading to large coexistence regions of different phases. This is evidently due to the simultaneous occupancy of anion tetrahedra by different numbers of Cl and Br atoms. The non-equivalent ZnX₄-tetrahedra of solid solutions do not suppress the occurence of the incommensurate phases. They exist between x = 0 to ?3 and are interrupted by a supposedly ferroelectric phase occuring up to x ?0.4. Around x ? 3 a triple point occurs the nature of which needs a closer elucidation.     

Crystal growth, spectroscopic and crystal field studies of [N(CH3)4]2MnCl4 and [N(CH3)4]2CoCl4 single crystals in the paraelectric phase

Single crystals [N(CH₃)₄]₂MnCl₄ and [N(CH₃)₄]₂CoCl₄ were grown by the slow evaporation technique from the super-saturated solutions. The samples obtained were undergone the X-ray and spectroscopic studies. Absorption spectra in the paraelectric phase at T=303 K have been recorded using the Shimadzu 160A double beam automatic scanning spectrophotometers. On the basis of the exchange charge model and Racah theory the crystal field parameters and Racah parameters have been calculated; all absorption bands for both crystals were given an assignment.     

Third-order nonlinearity and optical limiting of dichloromethane solutions of cis-Mo(CO)4(PPh3)2

Oxidized dichloromethane solutions of cis-Mo(CO)₄(PPh₃)₂ stabilized by the addition of excess PPh₃ exhibit unusual large molecular second-order hyperpolarizabilities with minimal linear absorption. To better understand the mechanism by which this occurs, DFWM, Z-scan and optical limiting experiments have been carried out on oxidized dichloromethane solutions of cis-Mo(CO)₄(PPh₃)₂ using 5.8 ns laser pulses at 532 nm. Our results demonstrate that the mechanism by which the oxidized species enhance the third-order nonlinear response is not dominated by thermal effects, but is instead due to the strong nonlinear absorption and nonlinear refraction of the oxidized species. Moreover, the oxidized species shows very strong optical limiting properties. Such complexes would be very interesting third-order nonlinear optical materials for optical limiting applications.     

Chlorine K X-ray absorption-edge structures of CIS-[Pt(NH3)2Cl2], trans-[Pt(NH3)2Cl2], trans-[Pd(NH3)2Cl2] and (NH4)2PdCl4

The K absorption-edge spectra of the ligand chlorine ion in square-planar complex compounds cis- and trans-[Pt(NH₃)₂Cl₂], trans-[Pd(NH₃)₂Cl₂], and (NH₄)₂PdCl₄ are reported and discussed in connection with the chlorine K absorption spectra of K₂PtCl₄ and K₂PdCl₄, reported previously. The observed chemical shift of a white line at the absorption threshold is interpreted in terms of the difference of the ligand-field splitting of electronic states for metal ions. The white line is attributed to the electronic transition from the Cl^? ls level to the lowest unoccupied antibonding molecular orbital (MO), which is specified by a $\text{MO}\text{b}{}_{\mathrm{1g}}\text{(σ}{}^1\text{)}$ in the square-planar complex with D_4h symmetry. The other absorption structures are regarded as continuum “shape resonances” of the outgoing electron trapped by the cage of the surrounding atoms. The effect of geometrical isomerism is found in the chlorine K absorption spectra of cis- and trans-[Pt(NH₃)₂Cl₂].     

Characterization of new-layered Cr(III)-doped chlorocadmiumphosphate, Cd(HPO4)Cl·[H3N(CH2)6NH3]0.5 crystal by EPR and optical studies

Cr(III)-doped Cd(HPO₄)Cl·[H₃N(CH₂)₆NH₃]_0.5, a new-layered cadmium phosphate, is synthesized in acidic condition at room temperature. EPR and optical studies are carried out at room temperature. Polycrystalline EPR spectrum reveals the presence of two sites of Cr(III) ions in this layered phosphate lattice with zero-field splitting values of 24.24 and 7.65 mT, indicating that Cr(III) ions are in distorted octahedral sites. The optical absorption spectrum of the sample indicates near octahedral symmetry for the dopant ions. Crystal field, inter-electronic and bonding parameters are evaluated by collaborating EPR and optical data. The evaluated parameters suggest the mode of entry of Cr(III) ion into the layered phosphate as interstitial site, and bonding between the metal and ligand is partially covalent.     

Linear and nonlinear optical properties of Ca3(VO4)2

Single crystals of Ca₃ (VO₄)₂ have been grown by the Czochralski method. The refractive indices show that the crystals are phasematchable between 1.72 μm and 2.94 μm with favourable values for acceptance angle and spectral width of the incident laser beam in the entire phasematching range. The nonlinear optical coefficients have been measured by the Maker fringe method at a fundamental wavelength of 1.064 μm. They are comparable to those of KDP. Thus the crystals are potentially useful for frequency conversion of broadband or tunable laser sources as semiconductor and F-center lasers. They may also be installed in high f-number IR image converters.