Studying the first order hyperpolarizability spectra in chalcone-based derivatives and the relation with one- and two-photon absorption transitions.

The first-order molecular hyperpolarizability (ß) dispersion was measured in seven chalcone-based molecules utilizing the tunable femtosecond hyper-Rayleigh scattering (tHRS) technique. Additionally, a theoretical model based on photophysical parameters was employed to better understand ß dispersion. Due to the distinct substitution patterns of the aryl/heteroaryl rings within the chalcone structure, varying profiles of one- and two-photon absorption spectra and ß dispersion were observed. The applied model highlighted two important factors contributing to achieving high ß values: (i) the presence of red-shifted one-photon and two-photon absorption bands; and (ii) the number of discernible absorption bands. To contextualize these results with other molecular structures, we employed the HRS figure of merit (FOM). Remarkably, it was revealed that chemically engineered small chalcone molecules exhibit a FOM comparable to larger quadrupolar and octupolar ones. This underscores the significance of tHRS scattering measurements and their correlation with absorptive parameters in the design and characterization of nonlinear optical materials.

Observation of the two-photon transition enhanced first hyperpolarizability spectra in cinnamaldehyde derivatives: A femtosecond regime study.

The application of nonlinear optical effects in optoelectronic devices is still scarce because the irradiance threshold necessary to induce a specific effect is very high. In this context, knowing the frequency-resolved first order molecular hyperpolarizability (ß) is essential to identifying regions where this response is intense enough to allow for applications in commercial devices. Thus, herein, we have determined the ß spectral dependence of five new push-pull cinnamylidene acetophenone derivatives using femtosecond laser-induced Hyper-Rayleigh Scattering (HRS). A considerable increase in ß values was observed in molecules. We found remarkable ß values in regions near the two-photon resonance, which are mediated by electron withdrawing and donating groups. This effect was mapped using wavelength-tunable femtosecond Z-scan technique. Furthermore, it was modeled in light of the sum-over-states approach for the second- and third-order nonlinearities. Finally, our outcomes suggest a strategy to obtain large ß values mediated by the 2PA transition.

Size-dependent photoinduced transparency in colloidal CdTe quantum dots in the strong confinement regime: an inverse linear relationship.

Nanomaterials have been investigated as saturable absorbers for ultrafast lasers because of their large photoinduced transparency related to ground-state bleaching. However, the quantum dot size effect on the photoinduced transparency in the strong confinement regime has not been explored due to the challenge of accurately measuring the ground state and the excited-state absorption cross-sections. At the same time, these optical properties are essential to calculate several chemical and physical quantities at the nanoscale. In this context, we have employed the photoluminescence saturation method to determine the ground-state absorption cross-section and the femtosecond open-aperture Z-scan technique to investigate the size-dependent ground-state bleaching of glutathione-capped CdTe QDs synthesized in an aqueous medium. The results were modeled using rate equations within the three-energy levels approach. Our results pointed out that the photoinduced transparency rate at the 1S3/2(h) → 1S(e) transition peak presents an inverse linear relationship with the QD diameter (from 2.2 nm up to 3 nm). Otherwise, the larger QDs have a higher ground-state cross-section, which is directly proportional to the ground-state bleaching. To explain this apparent contradiction, we calculate the effective absorption coefficient αeff = σ/V (σ is the absorption cross section and V is the QD volume) for the QDs and observed that the smaller QDs have a higher absorption from the ground to the first excited state, corroborating our results. Finally, our results showed that the saturable absorption effect in CdTe-QDs is slightly higher than that obtained for graphene and other 2D materials and smaller than the black phosphorus in the visible region.

Size-Dependent Photobleaching Mechanism and Kinetics Induced by Nanosecond Laser Pulses in Colloidal Semiconductor Quantum Dots.

An experimental-theoretical approach is proposed to investigate the size-dependent photobleaching of colloidal semiconductor quantum dots (QDs) excited by a nanosecond pulsed laser. In the experimental background, the ground-state absorption and photoluminescence (PL) spectra of chemically prepared QDs are monitored over an excitation time at distinct laser irradiances. The magnitude of photobleaching in the QD solution is quantified by the decay rate of the PL signal as a function of the excitation time and the laser power. A theoretical spectroscopy model is then used to estimate the particle size distribution (PSD) in colloidal solution from the absorption data generated at different laser powers. The resulting evolution of the PSD of the QD ensemble under irradiation is analyzed in terms of classical crystallization theories dealing with the formation, growth, and dissolution of colloidal particles in a supersaturated medium. The QD response to laser irradiation is also interpreted by a simple mechanical model that correlates the photoinduced hydrostatic strain at the solid/liquid interface and the predicted variation of the mean particle size. The reported experimental and theoretical methods are used to completely elucidate the basic physico-chemical processes responsible for the laser-induced photobleaching kinetics of glutathione-capped CdTe aqueous QDs with very small mean sizes. For this purpose, we synthesized a series of colloidal QD samples with mean particle diameters ranging from 1.95 to 2.68 nm. Our results indicate that a faster photobleaching rate occurs in QD samples with smaller sizes in which particle dissolution under laser irradiation is predominant. On the other hand, the photobleaching rate becomes slower in samples with larger dot sizes, possibly due to the formation of core/shell structures in solution via thermal degradation of thiol ligands either during the chemical synthesis or as a consequence of the subsequent interaction with the excitation laser.

Modeling the First-Order Molecular Hyperpolarizability Dispersion from Experimentally Obtained One- and Two-Photon Absorption.

The search for optical materials, particularly organic compounds, is still an attractive and essential field for developing several photonic devices and applications. For example, some applications are based on light scattering with twice the energy of the incoming photon for selected compounds, that is, the nonlinear optical effect related to the second-order susceptibility term from the electronic polarization expression. The microscopic interpretation of this phenomenon is called the first-order molecular hyperpolarizability or incoherent second harmonic generation of light. Understanding such phenomena as a function of the incoming wavelength is crucial to improving the optical response of future materials. Still, the experimental apparatus, hyper-Rayleigh scattering, apparently simple, is indeed a challenging task. Therefore, we proposed a proper alternative to obtain the dispersion of the first-order hyperpolarizability using the well-known one- and two-photon absorption techniques. By the spectral analysis of both the spectra, we gathered spectroscopic parameters and applied them for predicting the first-order hyperpolarizability dispersion. This prediction is based on an n-level energy system, taking into account the position and magnitude of transition dipole moments and the difference between the permanent dipole moment of the n-excited states. Moreover, using the presented method, we can avoid underestimating the first-order hyperpolarizability by not suppressing higher-energy transitions. Quantum chemical calculations and the hyper-Rayleigh scattering technique were used to validate the proposed method.