Nonlinear Optical Properties of Novel Metallophthalocyanines

Journal of Applied Spectroscopy - Detailed measurements of nonlinear optical properties and optical limiting for four phthalocyanine (Pc) derivatives (PcCo, PcCu, PcMn, and PcSi) are reported. The...     

The hidden property of Arrhenius-type relationship for the PSSNa–DMF/W solution

The effects of temperature and concentration on the reduced electrical conductivity of solutions of poly-(sodium styrene sulfonate) (PSSNa) in N,N-dimethylformamide + water were examined at different temperatures between 20 and 60°C and concentrations levels between 0.1 and 1 g/l. The effects of temperature were described by an Arrhenius-type equation. The intrinsic conductivities [σ] and the Huggins constant k_hσ of PSSNa were calculated and studied. Then, dln[σ]/d(1/T) was calculated as the indices for chain ?exibility and molecule conformation, respectively.

These results showed that the intrinsic electrical conductivities decreased linearly with increasing temperature, for all concentrations of PSSNa.     

Spectroscopic investigation of the chromium-doped LiNbGeO5 laser crystal

Polarized absorption and emission spectra, and temperature dependences of the fluorescence lifetimes and intensities for the chromium-doped LiNbGeO₅ laser crystal are presented. Crystal symmetry and comparison with the infrared fluorescence properties of the Cr-doped Mg₂SiO₄ and Y₃Al₅O₁₂ laser crystals seem to identify the active center as a Cr⁴⁺ ion in a tetrahedral site.     

Ultrafast shock compression and shock-induced decomposition of 1,3,5-triamino-2,4,6-trinitrobenzene subjected to a subnanosecond-duration shock: an analysis of decomposition products

Shock compression studies of pressed and confined ultrafine 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) powder were conducted using ultrashort ~300 ps, ~50 GPa shock waves. The recovered decomposition products were characterized using X-ray photoelectron spectroscopy, infrared spectroscopy, and Raman spectroscopy. A substantial amount of shock-related chemistry was observed. Approximately 75% of the nitrogen atoms were liberated as gas-phase species, along with ~33% of the oxygen atoms, as a result of the applied shock. Furthermore, we observe C 1s binding energies suggesting the formation of sp(3) hybridized amorphous carbon. For comparison, a carbon nitride material was also prepared and characterized by thermally pyrolizing TATB. The shock-compressed TATB and the thermally pyrolized TATB are qualitatively different, suggesting that, carbon nitrides, a possible indicator of nitrogen-rich heterocycles precursors, are not a major product class for strongly overdriven shock conditions. These experimental conditions were, however, not detonation conditions, and the possible formation of nitrogen-rich heterocycles in actual detonations still exists.     

Excited-state absorption of Co2+ in MgF2 and KZnF3

We report on measurements of excited-state absorption spectra and absolute cross-sections in Co²⁺-doped KZnF₃ and MgF₂ at room temperature in the near-infrared domain. The data are compared with the predictions of the single-configuration co-ordinate model.     

Effective Stimulated Emission Cross-Sections of Poly(Phenylene Vinylene) Copolymers in Toluene Solution

We report optical gain measurements in four different copolymers polyp-phenylene-co-[2,5-dioctyloxy-p-phenylene-bis-2(4-nonyl phenyl) vinylene]nonyl-PpPV, polym-phenylene-co-[2,5-dioctyloxy-p-phenylene-bis-2(4-methyl phenyl) vinylene]methyl-PmPV, polyp-phenylene-co-[2,5-dioctyloxy-p-phenylene-bis-2(4-methyl-phenyl) vinylene]methyl-PpPV, polyp-phenylene-co-[2,6-naphthylene-bis-2(4-nonyl phenyl) vinylene]nonyl-PpPV-NV in toluene. The copolymers are related to poly(phenylene vinylene) and have been synthesized via Horner–Emmons polycondensation reaction. The optical gain determined from the amplified spontaneous emission (ASE) intensity is dependent on the excited stripe length. The net optical gain coefficients are found to vary between 0.1 cm^–1 in nonyl-PpPV to 2.5 cm^–1 in methyl-PmPV under nanosecond pulse excitation. The gain for Rodamine 6G was also measured under the same experimental condition and was used to determine the stimulated emission cross-sections for the four polymers and found to be _SE(peak)= 6.7 × 10^–20 cm² for nonyl-PpPV, _SE(peak)= 1.7 × 10¹⁸ cm² for methyl-PmPV, _SE(peak)= 1.4 × 10^–18 cm² for methyl-PpPV, and _SE(peak)= 1.5 × 10^–18 cm² for nonyl-PpPV-NV.     

Nonlinear optical properties of Cr<Superscript>3+</Superscript>-doped laser crystals

The nonlinear optical properties in six Cr³⁺-doped laser crystals LiCaAlF₆, LiSrGaAlF₆, Gd₃Ga₅O₁₂, Gd₃Sc₂Ga₃O₁₂, LaMgAl₁₁O₁₉ and Alexandrite are investigated with the help of the Z-Scan technique at λ = 532 nm in the CW regime. The data reported here include particularly the excited state absorption cross section and the third-order nonlinear susceptibilities. It is found that the three first systems only exhibit both refractive and absorptive nonlinear effects, whereas the three others have only absorptive effects. Gd₃Ga₅O₁₂ shows the best nonlinear potentialities. The excited state absorption cross section corresponding mainly to the ⁴T₂ →   ⁴T₁ transition is found to be ranging between 8.9 × 10⁻²² cm² in LiSGaF and 3.1 × 10⁻²⁰ cm² in LaMgAl₁₁O₁₉. The calculated ratio of the third order nonlinear susceptibility to the ground state absorption coefficient is found to be largest in GGG with a value of 146 × 10⁻⁶ esu.cm and smallest in Alexandrite (0.6 × 10⁻⁶ esu.cm).     

Adsorption of hydrogen in defective carbon nanotube: modelling and consequent investigations using statistical physics formalism

ABSTRACT

Experimental adsorption isotherms of hydrogen in CNT samples (CNT-A, activated CNT-A CNT-B and activated CNT-B) at T?=?77, 87 and 90?K have been fitted using some theoretical model expressions treated by statistical physics through the grand canonical ensemble. The monolayer model with single energy is selected to fit and interpret the experimental data obtained with CNTs. The physico-chemical parameters, interfering in the adsorption process and implicated in the model expressions, could be directly determined from the experimental data through numerical simulation. Three parameters of the model are fitted, namely the number of hydrogen molecule per site n, the interstitial site density N_m and the energetic parameter P_1/2. The evolution of these parameters as function of temperature is plotted and interpreted in relation to adsorption process. Finally, the thermo-dynamic potential functions, which involve in the adsorption mechanism like free enthalpy of Gibbs G_a, internal energy E_int and entropy S_a, are derived by statistical physics calculations from the selected model.     

Excitations, optical absorption spectra, and optical excitonic gaps of heterofullerenes. I. C60, C59N+, and C48N12: theory and experiment

Low-energy excitations and optical absorption spectrum of C(60) are computed by using time-dependent (TD) Hartree-Fock, TD-density functional theory (TD-DFT), TD DFT-based tight-binding (TD-DFT-TB), and a semiempirical Zerner intermediate neglect of diatomic differential overlap method. A detailed comparison of experiment and theory for the excitation energies, optical gap, and absorption spectrum of C(60) is presented. It is found that electron correlations and correlation of excitations play important roles in accurately assigning the spectral features of C(60), and that the TD-DFT method with nonhybrid functionals or a local spin density approximation leads to more accurate excitation energies than with hybrid functionals. The level of agreement between theory and experiment for C(60) justifies similar calculations of the excitations and optical absorption spectrum of a monomeric azafullerene cation C(59)N(+), to serve as a spectroscopy reference for the characterization of carborane anion salts. Although it is an isoelectronic analogue to C(60), C(59)N(+) exhibits distinguishing spectral features different from C(60): (1) the first singlet is dipole-allowed and the optical gap is redshifted by 1.44 eV; (2) several weaker absorption maxima occur in the visible region; (3) the transient triplet-triplet absorption at 1.60 eV (775 nm) is much broader and the decay of the triplet state is much faster. The calculated spectra of C(59)N(+) characterize and explain well the measured ultraviolet-visible (UV-vis) and transient absorption spectra of the carborane anion salt [C(59)N][Ag(CB(11)H(6)Cl(6))(2)] [Kim et al., J. Am. Chem. Soc. 125, 4024 (2003)]. For the most stable isomer of C(48)N(12), we predict that the first singlet is dipole-allowed, the optical gap is redshifted by 1.22 eV relative to that of C(60), and optical absorption maxima occur at 585, 528, 443, 363, 340, 314, and 303 nm. We point out that the characterization of the UV-vis and transient absorption spectra of C(48)N(12) isomers is helpful in distinguishing the isomer structures required for applications in molecular electronics. For C(59)N(+) and C(48)N(12) as well as C(60), TD-DFT-TB yields reasonable agreement with TD-DFT calculations at a highly reduced cost. Our study suggests that C(60), C(59)N(+), and C(48)N(12), which differ in their optical gaps, have potential applications in polymer science, biology, and medicine as single-molecule fluorescent probes, in photovoltaics as the n-type emitter and/or p-type base of a p-n junction solar cell, and in nanoelectronics as fluorescence-based sensors and switches.     

Flash ignition and initiation of explosives-nanotubes mixture

Optical ignition and initiation of energetic materials could thus far be only accomplished through lasers, with specific characteristics of high power, pulse length, wavelength, and a small target area that greatly inhibit their applications. Here, we report that an ignition and an initiation process, further leading to actual detonation, does occur for energetic materials in lax contact with carbon nanotubes that are prone to opto-thermal activity via a conventional flashbulb. Our results show that, for the first time, optical initiation of energetic materials is possible on a large surface area and using ordinary light intensity of several W/cm2. The implication is that energetic materials mixed with optically active nanotubes could be new ideal candidates for safety apparatus, such as the firing of bolts on space shuttle rockets and aircraft exit doors.