Effect of Mercaptosuccinic Acid Stabilizer Agent on the Optical Properties of Colloidal CdTe Quantum Dots.

In the present work, we report on the positive effect of mercaptosuccinic acid (MSA) stabilizer agent on the optical features of colloidal CdTe quantum dots (QDs). With this aim, we performed some spectroscopic measurements such as steady-state absorption and fluorescence, fluorescence quantum yield and time-resolved photoluminescence for five MSA-capped CdTe QD samples with different synthesis times. The first general aspect to highlight is that the QDs' average size increased with synthesis time (from 30 to 150 min) while the size dispersion decreased due to the Ostwald ripening mechanism. Second, comparing the optical properties of CdTe QDs obtained from the same synthesis route, we show that MSA stabilizer agent enhanced the optical properties of CdTe QDs as compared with other widely used stabilizer agents such as GSH and TGA. We ascribe this outcome to reduction of the number of surface defects of the CdTe QDs because the MSA stabilizer agent decreases the growth rate of nanocrystals, causing an improvement in their surface quality. In the light of Fermi's golden rule, we observed that for longer synthesis time the optical properties of CdTe QDs increases due to the enhancement of the direct radiative recombination rate of electrons and holes and decrease in the decay rate for core states. Finally, we investigated the pH-dependent fluorescence and demonstrated the similar behaviour in acidic range between MSA-capped CdTe and mercaptocarboxylates-capped CdTe.

Effect of solvent-induced coil to helix conformational change on the two-photon absorption spectrum of poly(3,6-phenanthrene).

This paper investigates the effect of solvent-induced conformational changes of poly(3,6-phenanthrene) on their two-photon absorption (2PA). Such effect was studied employing the wavelength-tunable femtosecond Z-scan technique and modeled using the sum-over-essential states approach. We observed a strong reduction of the 2PA cross-section when the sample was prepared in hexane (poor solvent) in comparison to chloroform (good solvent), which is related to the conformation adopted by the polymer in each case. In chloroform it adopts a random coil conformation, as opposed to the one-handed helix conformation in hexane. Our results pointed out that the coil to helix conformation change decreases the degree of molecular planarity of the polymer π-conjugated backbone, which is primarily responsible for their optical nonlinearity, contributing to diminishing the effective transition dipole moments and, consequently, the 2PA cross-section. Moreover, by studying the nonlinear response with different light polarization, we showed that, although the solvent-induced conformational change does not alter the molecular symmetry of the polymer, it modifies considerably the direction of the transition dipole moments between the excited states.

Polarization effect on the two-photon absorption of a chiral compound.

In this report, we investigate the polarization effect (linear, elliptical and circular) on the two-photon absorption (2PA) properties of a chiral compound based in azoaromatic moieties using the femtosecond Z-scan technique with low repetition rate and low pulse energy. We observed a strong 2PA modulation between 800 nm and 960 nm as a function the polarization changes from linear through elliptical to circular. Such results were interpreted employing the sum-over-essential states approach, which allowed us to model the 2PA circular-linear dichroism effect and to identifier the overlapping of the excited electronic states responsible by the 2PA allowed band.

Temperature effect on the two-photon absorption spectrum of all-trans-ß-carotene.

In this report, we investigate the influence of temperature on the two-photon absorption (2PA) spectrum of all-trans-ß-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.

Femtosecond laser induced synthesis of Au nanoparticles mediated by chitosan.

This paper reports the synthesis of Au nanoparticles by 30-fs pulses irradiation of a sample containing HAuCl4 and chitosan, a biopolymer used as reducing agent and stabilizer. We observed that it is a multi-photon induced process, with a threshold irradiance of 3.8 × 10(11) W/cm2 at 790 nm. By transmission electron microscopy we observed nanoparticles from 8 to 50 nm with distinct shapes. Infrared spectroscopy indicated that the reduction of gold and consequent production of nanoparticles is related to the fs-pulse induced oxidation of hydroxyl to carbonyl groups in chitosan.

Linear and nonlinear optical properties of the thiophene/phenylene-based oligomer and polymer.

In this article, we investigate the linear and nonlinear optical properties of the thiophene/phenylene-based oligomer (SL128G) and polymer (FSE59) chemically modified with alquilic chains, which allow greater solubility and provide new optical properties. These compounds present a strong absorption in the UV-visible region, providing a wide transparence window in visible-IR, ideal for applications in nonlinear optics. Employing the Z-scan technique with femtosecond pulses, we show that these compounds exhibit considerable two-photon absorption (2PA), with two 2PA allowed states located at 650 and 800 nm for SL128G and 780 and 920 nm for FSE59. Moreover, we observe the resonance enhancement effect as the excitation wavelength approaches the lowest one-photon-allowed state. By modeling the 2PA spectra considering a four-energy-level diagram within of the sum-over-essential states approach, we obtained the spectroscopic parameters of the electronic transitions to low-energy singlet excited states. Additionally, photoluminescence excited by femtosecond and picosecond pulses were performed to confirm the order of the multiphoton process and estimate the fluorescence lifetime, respectively.

Nonlinear spectra of ZnO: reverse saturable, two- and three-photon absorption.

We present a broadband (460 - 980 nm) analysis of the nonlinear absorption processes in bulk ZnO, a large-bandgap material with potential blue-to-UV photonic device applications. Using an optical parametric amplifier we generated tunable 1-kHz repetition rate laser pulses and employed the Z-scan technique to investigate the nonlinear absorption spectrum of ZnO. For excitation wavelengths below 500 nm, we observed reverse saturable absorption due to one-photon excitation of the sample, agreeing with rate-equation modeling. Two- and three-photon absorption were observed from 540 to 980 nm. We also determined the spectral regions exhibiting mixture of nonlinear absorption mechanisms, which were confirmed by photoluminescence measurements.

Degenerate two-photon absorption in all-trans retinal: nonlinear spectrum and theoretical calculations.

In this work we investigate the degenerate two-photon absorption spectrum of all-trans retinal in ethanol employing the Z-scan technique with femtosecond pulses. The two-photon absorption (2PA) spectrum presents a monotonous increase as the excitation wavelength approaches the one-photon absorption band and a peak at 790 nm. We attribute the 2PA band to the mixing of states (1)B(u)(+)-like and |S(1)>, which are strongly allowed by one- and two-photon, respectively. We modeled the 2PA spectrum by using the sum-over-states approach and obtained spectroscopic parameters of the electronic transitions to |S(1)>, |S(2)> ("(1)B(u)(+)"), |S(3)>, and |S(4)> singlet-excited states. The results were compared with theoretical predictions of one- and two-photon transition calculations using the response functions formalism within the density functional theory framework with the aid of the CAM-B3LYP functional.