Investigation of Ground- and Excited-State Photophysical Properties of 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphyrin with Ruthenium Outlying Complexes

The present work employs a set of complementary techniques to investigate the influence of outlying Ru(II) groups on the ground- and excited-state photophysical properties of free-base tetrapyridyl porphyrin (H(2)TPyP). Single pulse and, pulse train Z-scan techniques used M association with laser flash photolysis, absorbance and fluorescence spectroscopy, and fluorescence decay measurements, allowed us to conclude that the presence of outlying Ru(II) groups causes significant changes on both electronic structure and vibrational properties of porphyrin. Such modifications take place mainly due to the activation of. nonradiative decay channels responsible for the emission, quenching, as well as by favoring some vibrational modes in the light absorption process, It is also observed that, differently from what happens when the Ru(II) is placed at the center of the macrocycle, the peripheral groups cause an increase of the intersystem crossing processes, probably due to the structural distortion of the ring that implies a worse spin orbit coupling, responsible for the intersystem crossing mechanism.

Temperature Effect on the Two-Photon Absorption Spectrum of All-trans-beta-carotene

In this report, we investigate the influence of temperature on the two-photon absorption (2PA) spectrum of all-trans-beta-carotene using the femtosecond white-light-continuum Z-scan technique. We observed that the 2PA cross-section decreases quadratically with the temperature. Such effect was modeled using a three-energy-level diagram within the sum-over-essential states approach, assuming temperature dependencies to the transition dipole moment and refractive index of the solvent. The results show that the transition dipole moments from ground to excited state and between the excited states, which governed the two-photon matrix element, have distinct behaviors with the temperature. The first one presents a quadratic dependence, while the second exhibits a linear dependence. Such effects were attributed mainly to the trans -> cis thermal interconversion process, which decreases the effective conjugation length, contributing to diminishing the transition dipole moments and, consequently, the 2PA cross-section.

Excited-state dynamics of meso-tetrakis(sulfonatophenyl) porphyrin J-aggregates

The excited-state dynamics of free-base meso-tetrakis(sulfonatophenyl) porphyrin J-aggregates obtained by the Z-scan technique in femto- and picosecond time scales, along with UV-Vis spectroscopy and flash photolysis is reported. Besides obtaining the S-1 state lifetime, the discrimination between internal conversion and intersystem crossing nonradiative processes from that state was also possible, and their rates and respective quantum yields were found. The aggregates present reverse saturable absorption at 532 nm for both singlet and triplet excited states. The data shown is important for several applications such as optical limiting, photodynamic therapy and others. (C) 2011 Elsevier B.V. All rights reserved.

Transverse pseudo-nonlinear effects measured in solid-state laser materials using a sensitive time-resolved technique

We present a detailed study of the Baryscan technique, a new efficient alternative to the widespread Z-scan technique which has been demonstrated [Opt. Lett. 36:8, 2011] to reach among the highest sensitivity levels. This method is based upon the measurement of optical nonlinearities by means of beam centroid displacements with a position sensitive detector and is able to deal with any kind of lensing effect. This technique is applied here to measure pump-induced electronic refractive index changes (population lens), which can be discriminated from parasitic thermal effects by using a time-resolved Baryscan experiment. This method is validated by evaluating the polarizability variation at the origin of the population lens observed in the reference Cr3+:GSGG laser material.

Two-photon absorption in oxazole derivatives: An experimental and quantum chemical study

Experimental and theoretical studies on the two-photon absorption properties of two oxazole derivatives: 2,5-diphenyloxazole (PPO) and 2-(4-biphenylyI)-5-phenyl-1,3,4-oxadiazole (PBD) are presented. The two-photon absorption cross-section spectra were determined by means of the Z-scan technique, from 460 up to 650 nm, and reached peak values of 84 GM for PBD and 27 GM for PPO. Density Functional Theory and response function formalism are used to determine the molecular structures and the one- and two-photon absorption properties and to assist in the interpretation of the experimental results. The Polarizable Continuum Model in one-photon absorption calculations is used to estimate solvent effects. (C) 2011 Elsevier B.V. All rights reserved.

Modulation transfer function and optical quality after bilateral implantation of a+3.00 D versus a+4.00 D multifocal intraocular lens

PURPOSE: To determine whether the improvement in intermediate vision after bilateral implantation of an aspheric multifocal intraocular lens (IOL) with a +3.00 diopter (D) addition (add) occurs at the expense of optical quality compared with the previous model with a +4.00 D add. SETTING: Department of Ophthalmology, University of Sao Paulo, Sao Paulo, Brazil. DESIGN: Prospective randomized double-masked comparative clinical trial. METHODS: One year after bilateral implantation of Acrysof Restor SN6AD1 +3.00 D IOLs or Acrysof Restor SN6AD3 +4.00 D IOLs, optical quality was evaluated by analyzing the in vivo modulation transfer function (MTF) and point-spread function (expressed as Strehl ratio). The Strehl ratio and MTF curve with a 4.0 pupil and a 6.0 mm pupil were measured by dynamic retinoscopy aberrometry. The uncorrected and corrected distance visual acuities at 4 m, uncorrected and distance-corrected near visual acuities at 40 cm, and uncorrected and distance-corrected intermediate visual acuities at 50 cm, 60 cm, and 70 cm were measured. RESULTS: Both IOL groups comprised 40 eyes of 20 patients. One year postoperatively, there were no statistically significant between-group differences in the MTF or Strehl ratio with either pupil size. There were no statistically significant between-group differences in distance or near visual acuity. Intermediate visual acuity was significantly better in the +3.00 D IOL group. CONCLUSION: Results indicate that the improvement in intermediate vision in eyes with the aspheric multifocal +3.00 D add IOL occurred without decreasing optical quality over that with the previous version IOL with a +4.00 D add.

Two-photon excitation and optical limiting in polyfluorene derivatives

Fluorene-based polymers are widely known materials due to a combination of features such as photoluminescence and electroluminescence, oxidative stability, and film-forming ability. However, studies reporting nonlinear optical properties in this class of conjugated polymer are scarce. Here, we report a new class of polyfluorene derivatives poly(9,9'-n-dihexyl-2,7-fluorenedilvinylene-alt-1,4-phenylenevinylene), poly(9,9'-n-dihexyl-2,7-fluorenedilvinylene-alt-2,5-thiophene), and poly[(9,9-di-hexylfluorenediylvinylene-alt-1,4-phenylenevinylene)-co-((9,9'-(3-t-butylpropanoate) fluorene-1,4-phenylene)] displaying high two-photon absorption (2PA) in the spectral range from a 490 to 1100 nm. The 2PA cross-section peak values for these materials are as high as 3000 Goppert Mayer (1 GM = 1 x 10-50 cm4 s/photon), which is related to the high degree of conjugation along the polymer backbone. The polymers that were used in this study presented a strong two-photon luminescence and also displayed optical limiting behavior, which, in combination with their well-established properties, make them highly suitable for nonlinear optical devices. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 148153, 2012

Optical third harmonic generation in the magnetic semiconductor EuSe

Third harmonic generation (THG) has been studied in europium selenide EuSe in the vicinity of the band gap at 2.1-2.6 eV and at higher energies up to 3.7 eV. EuSe is amagnetic semiconductor crystalizing in centrosymmetric structure of rock-salt type with the point group m3m. For this symmetry the crystallographic and magnetic-field-induced THG nonlinearities are allowed in the electric-dipole approximation. Using temperature, magnetic field, and rotational anisotropy measurements, the crystallographic and magnetic-field-induced contributions to THG were unambiguously separated. Strong resonant magnetic-field-induced THG signals were measured at energies in the range of 2.1-2.6 eV and 3.1-3.6 eV for which we assign to transitions from 4 f(7) to 4 f(6)5d(1) bands, namely involving 5d(t(2g)) and 5d(e(g)) states.

Application of the Z-scan technique to determine the optical Kerr coefficient and two-photon absorption coefficient of magnetite nanoparticles colloidal suspension

We investigate the occurrence of the optical Kerr effect and two-photon absorption when an oil-based magnetic Fe3O4 nanoparticles colloidal suspension is illuminated with high intensity femtosecond laser pulses. The frequency of the pulses is controlled and the Z-scan technique is employed in our measurements of the nonlinear optical Kerr coefficient (n(2)) and two-photon absorption coefficient (beta). From these values it was possible to calculate the real and imaginary parts of the third-order susceptibility. We observed that increasing the pulse frequency, additional physical processes take place, increasing artificially the absolute values of n(2) and beta. The experimental conditions are discussed to assure the obtention of reliable values of these nonlinear optical parameters, which may be useful in all-optical switching and optical power limiting applications. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4723829]

Effect of interaction with micelles on the excited-state optical properties of zinc porphyrins and J-aggregates formation

This work reports on the photophysical properties of zinc porphyrins meso-tetrakis methylpyridiniumyl (Zn2+TMPyP) and meso-tetrakis sulfonatophenyl (Zn2+TPPS) in homogeneous aqueous solutions and in the presence of sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) micelles. The excited-state dynamic was investigated with the Z-scan technique, UV-Vis absorption, and fluorescence spectroscopy. Photophysical parameters were obtained by analyzing the experimental data with a conventional five-energy-level diagram. The interaction of the charged side porphyrin groups with oppositely charged surfactants can reduce the electrostatic repulsion between porphyrin molecules leading to aggregation, which affected the porphyrin characteristics such as absorption cross-sections, lifetimes and quantum yields. The interaction between anionic ZnTPPS with cationic CTAB micelles induced the formation of porphyrin J-aggregates, while this effect was not observed in the interaction of ZnTMPyP with SDS micelles. This difference is, probably, due to the difference in electrostatic repulsion between the porphyrin molecules. The insights obtained by these results are important for the understanding of the photophysical behavior of porphyrins, regarding potential applications in pharmacokinetics as encapsulation of photosensitizer for drug delivery systems and in its interaction with cellular membrane.