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Organic molecules have been intensively studied during the last few decades because of their photonics and biological applications.

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 1S

Semiconductor polymers are the foundation of organic electronics due to their remarkable optical features, ability to form a thin film, and low cost compared to silicon. However, some of them have intense photobleaching under UV-blue radiation, compromising several applications. In this context, we have investigated the conformational disorder effect on the real-time photobleaching kinetics of a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV)/chloroform solution under deep-blue radiation. Our results pointed out that a 405 nm diode laser initially causes a significant conformational disorder in the π-conjugated backbone of MEH-PPV as revealed by the Huang-Rhys factor. As a result, a new vibrational mode arises with an energy separation of 230 meV, indicating the substitution of the vinyl (C═C) by carbonyl (C═O) bonds. Then, the conformational disorder reaches a maximum value at some tens of minutes, which is inversely proportional to the polymer concentration, and after that, a random chain scission occurs. Consequently, the effective conjugation length of MEH-PPV in chloroform decreases from nine to three coplanar repetitive units after 1 h of excitation, producing a drastic drop in photoluminescence. Finally, we show that the photobleaching steps are mapped through the conformational disorder.

Laser Microfabrication (LMF) has been widely employed in a broad range of applications based on linear and nonlinear optics phenomena. Thus, this work aims to develop an Arduino-controlled low-cost LMF setup with high quality and precision. The LMF setup comprises a homemade optical microscope, a motorized 3-D translation stage based on low-cost stepper motors and current driver, and a relay module to control the hard disk shutter switch. We show that the microfabrication setup is capable of a precise XY translation motion with 25 mm travel range and scanning speeds as high as 1350 μm/s, with a resolution of 315 nm while presenting high precision and repeatability (tiny backlash

Chitosan (CS) is a biopolymer that presents remarkable biomedical applications. Here we report on the fluorescence study of water-soluble CS nanoparticles obtained by hydrothermal treatment at diff...

We determine the two-photon absorption (2PA) cross section spectra branched polyfluorenes distinguished by the number of fluorenes and chemical architecture. Moreover, the optical properties were determined in function of the effective electrons number of each compound.

Fluorene-based molecules exhibit significant nonlinear optical responses and multiphoton absorption in the visible region, which, combined with the high fluorescence quantum yield in organic solvents, could make this class of materials potentially engaging in diverse photonics applications. Thus, herein, we have determined the two-photon absorption (2PA) of oligofluorenes containing three, five, and seven repetitive units by employing the wavelength-tunable femtosecond Z-scan technique. Our outcomes have shown that the 2PA cross-section in oligofluorenes presents an enhanced value of around 18 GM per Neff, in which Neff is the effective number of π-electrons, for the pure 2PA allowed transition (11Ag-like → 21Ag-like). Furthermore, a weak 2PA transition was observed in the same spectral region strongly allowed by one-photon absorption (11Ag-like → 11Bu-like). This last result suggests a molecular symmetry perturbation, probably induced by the molecular disorder triggered by the increase of moieties in the oligofluorene structure. We have calculated the permanent dipole moment difference related to the lowest-energy transition using the Lippert-Matagaformalism and the 2PA sum-over-states approach to confirm this assumption. Moreover, we have estimated the fundamental limits for the 2PA cross-section in oligofluorenes.

The first-order hyperpolarizability of π-conjugated organic molecules is of particular interest for the fabrication of electro-optical modulators. Thus, we investigated the relationship between the molecular structure and the incoherent second-order nonlinear optical response (βHRS) of four salicylidene derivatives (salophen, [Zn(salophen)(OH2)], 3,4-benzophen, [Zn(3,4-benzophen)(OH2)]) dissolved in DMSO. For that, we employed the Hyper-Rayleigh Scattering technique with picosecond pulse trains. Our experimental results pointed out dynamic βHRS values between 32.0 ± 4.8 × 10-30 cm5/esu and 58.5 ± 8.0 × 10-30 cm5/esu at 1064 nm, depending on the molecular geometry of the salicylidene molecules. More specifically, the outcomes indicate a considerable increase of βHRS magnitude (∼30%) when in the ligands are incorporated the Zn(II) ion. We ascribed such results to the rise of the planarity of the π-conjugated backbone of the chromophores caused by the Zn(II). Furthermore, we observed an increase of ∼50% in dynamic βHRS when there is a replacement of one hydrogen atom (salophen molecule) by an acetophenone group (3,4-benzophen). This result is related to the increase of the effective π-electron number and the higher charge transfer induced at the excited state. All these findings were interpreted and supported in the light of time-dependent density functional theory (DFT) calculations. Solvent effects were considered in the quantum chemical calculations using the integral equation formalism variant of the polarizable continuum model.

Optical birefringence in polymeric films containing azo-chromophores is an important feature related to the development of several technologies such as electro-optic modulators, optical switching, and optical gates, to cite a few. Therefore, it is essential to understand the main underlying mechanisms describing dynamic switching. In this context, we have investigated the optical birefringence performance of a guest–host film produced from a poly(methyl methacrylate) (PMMA) matrix containing a V-shaped azo-chromophore, which exhibited a larger optical response in comparison to the linear chromophores. The optical birefringence was induced by a linearly polarized diode laser (532 nm, writing laser), while a low-intensity HeNe (632.8 nm) laser and a tungsten-halogen lamp are employed, respectively, to monitor the optical storage and the absorption change during the photoinduced birefringence. Our results pointed out that the guest–host film presents maximum residual optical memory at around 50% and local optical birefringence at around 3.3 × 10−4 in the low concentration and intensity regimes. The high optical birefringence obtained in guest–host films was attributed to the considerable photoisomerization quantum yield in the solid-state (0.15 ± 0.02 for 532 nm). Besides, we have shown that the switching mechanism is driven by angular hole-burning during the first seconds after excitation, and, subsequently, molecular reorientation quickly rises, dominating the photochemical process. The latter mechanism is highly efficient in converting cis to trans molecules (100%), which is responsible for the high residual optical memory obtained. In order to better understand the isomerization mechanism of the azo-chromophore/PMMA film, we performed quantum chemical calculations within the DFT framework. The electronic transitions of the azo-chromophore isomers were determined using the TD-DFT method and potential energy curves (PECs) were constructed to investigate the possibility of the thermal-isomerization process of the V-shaped azo-chromophore through both rotation and inversion mechanisms. For both mechanisms, the amplitude of the energy barrier and activation energy for thermal isomerization are determined and the results are discussed.

Due to their capability of film formation and remarkable optical features, semiconductor polymers with high two-photon absorption (2PA) have been studied as potential candidates for the development of organic photonic platforms. Furthermore, there is a high demand for photonic devices operating in the near-infrared (IR) region. However, the magnitude of the nonlinear optical response of random coil polymers in the IR region is weak due to the loss of molecular structure caused by increasing the π-conjugated backbone. Thus, herein we aim to investigate the molecular structure and 2PA features relationship for four polymers with supramolecular (helical) rodlike structure. Such polymers have a rigid core based on triphenylamine groups connected to the chiral binaphthalene units and a strong electron-withdrawing group (EWG). This kind of structure allows a very high chromophore density, which was responsible for generating 2PA cross-section between 305 GM and 565 GM in the near-IR (900-1300 nm), depending on the EWG strength. in light of the two-level model within the sum-overstates approach, we estimated the degree of intramolecular charge transfer induced by 2PA in the IR region, and values as high as 50-70% were found. Such a critical outcome allows the 2PA cross-section in the IR region to remain high even though the ratio between the visible/IR-band 2PA cross-section increases as a function of EWG strength.

Semiconductors thin films are the foundation of modern technology. While the nonlinear optical (NLO) properties of bulk semiconductors have been systematically studied in the last three decades, it is still a great challenge to obtain them for semiconductors thin films, as the high laser irradiance in NLO experiments tends to irreversibly damage the thin films. In addition, tuning the NLO response of semiconductor thin films by alloying and doping has not been explored yet. Here, we study the influence of the Aluminum content in AlxGa1-xN thin films and the n-type doping concentration in GaN thin films on their two-photon absorption (2PA) coefficients. For this, we investigate five different GaN-based thin films: an unintentionally doped one with no Al as a reference, two n-type doped GaN films with distinct concentrations of silicon impurities, and two AlxGa1-xN alloys with an aluminum content of 5.5% and 9.0%, respectively. The femtosecond 2PA spectra reveal that doping impurities reduce the non-linear coefficients (∼10%), while alloying with Al enhances the 2PA coefficient up to 30%. We use the model of Brandi and Araujo to determine Kane’s energy parameter related to the transition matrix element for each sample and compare them with recent theoretical studies based on the k·p theory where an excellent agreement is found.

Hyper-Rayleigh scattering (HRS) is a parametric optical effect in which two incident photons of frequency ω are annihilated to create a scattered photon of frequency 2ω. Unlike second harmonic generation (SHG), the HRS signal is isotropic, incoherent, and dephased with the excitation photon. HRS has been widely used to investigate novel materials with potential for the development of technologies, such as more efficient frequency doubling, high-resolution microscopy, fast electro-optic modulation, ultrafast lasers, and even to identify the interaction and affinity between biological molecules. In this chapter, we describe the potential of the HRS technique to investigate the first-order hyperpolarizability of organic molecules. For that, we initially present fundamentals of the first-order hyperpolarizability in materials. Theoretical approaches applied to estimate the first-order hyperpolarizability are also presented. These approaches employ different quantum chemical methods combined with a numerical or analytical scheme. Three of the most commonly used schemes, namely the finite field (FF) scheme, the sum-over-states (SOS) scheme, and the coupled-perturbed scheme, are briefly described. These approaches are used to aid in the understanding of the fundamental aspects that can be exploited, at the molecular level, to reach remarkable first-order hyperpolarizability (>10−27 cm5/esu). Moreover, we present in detail different experimental setups used to quantify in HRS experiments. Finally, recent results about the first-order hyperpolarizability are described and discussed for organic molecules with distinct molecular structures, as well as the use of the HRS effect as a technique to quantify specific interactions of biological materials.

International audience; In the present work, we report the multibranching effect on the dynamic first-order hyperpolarizability (β(−2ω; ω, ω)) of triphenylamine derivatives containing cyanopyridine one-branch (dipolar structure), two-branch (V-shaped structure), and three-branch (octupolar structure) structures. For this study, we used the hyper-Rayleigh scattering (HRS) technique involving picosecond pulse trains at 1064 nm. Our results show that βHRS increases from 2.02 × 10–28 to 9.24 × 10–28 cm5/esu when an extra branch is added to the molecule, configuring a change from a dipolar to a V-shaped (quadrupolar) molecular structure. When a third branch is added, leading to an octupolar structure, a decrease to 3.21 × 10–28 cm5/esu is observed. Such a significant decrease in βHRS is attributed to a negative contribution presented in the βHRS description by using a three-level energy approach due to their electronic structure and considering a specific combination of the angle between the dipole moments. On the other hand, the enhancement of βHRS found for the quadrupolar structure is associated with the cooperative enhancement due to the electronic coupling between the branches that increases considerably the transition dipole moment and permanent dipole moment change. To explain the βHRS results obtained for different molecules, we employed the HRS figure of merit, FOMHRS = βHRS/Neff3/2, in which Neff is the effective number of π-conjugated bonds, and the few-energy level approach for βHRS within the Frenkel exciton model. To shed more light on the experimental results interpretation, we performed time-dependent density functional theory calculations combined with a polarizable continuum model to confirm the energy and oscillator strength of the electronic transitions assumed in the Frenkel exciton model employed here.

The intramolecular cooperative effect in branched molecules is a consequence of the interaction and extent of electronic coupling among the different axes of charge transfer. Such an effect is the key to obtain remarkable nonlinear optical response in molecular systems. Here we show that triphenylamine derivative molecules containing only two branches present the strongest electronic interaction between them at the excited state, generating exponential enhancement of the 2PA cross section. The primary factor for such behavior was ascribed to the substantial extent and interaction of the π-electron delocalization promoted by the strong electron-donating and acceptor antisymmetrical groups present in each branch. However, for the three-branch molecules we observed an anticooperative effect, i.e., the 2PA cross section decreases as compared to the one-branch structure as we normalized the signal by the effective π-electron number in each molecule.

It has been a great challenge to measure the spectrum of pure bound-electronic third-order nonlinear refraction ( n2) of organic chromophores in solutions because of the spurious contribution from the solvent and cuvette walls. In order to circumvent this problem, we present here a new method to obtain a highly accurate absolute n2 value of organic molecules in solutions with a self-referenced nonlinear ellipse rotation (NER) technique. As a proof of concept, we measured n2 spectra of two well-known chromophores, rhodamines B and 6G dissolved in methanol, in the range from ∼600 to 1200 nm. Our results pointed out that these two dyes present similar dispersion curves with strong negative nonlinearities near the one-photon absorption band and small positive values at long wavelengths. Furthermore, the negative signal of the dyes can be strong enough to cancel and even invert the positive nonlinear refraction of the solvent (methanol) as the solution's concentration increases. To understand the n2 spectrum and its connection to molecular properties of organic chromophores, we employed the sum-over-states (SOS) approach within the few-energy-level model and observed an excellent agreement between the experimental and theoretical spectra. In this way, we believe that, employing our NER technique and the SOS model, it is possible to determine both experimentally and theoretically the absolute magnitude and spectra of pure electronic n2 for a large variety of other organic molecules.

Nonlinear absorption of GaN and AlxGa1-xN thin films were studied by the Z-scan technique in the range of 0.53~0.63 Ephoton/Eg, with values ranging from 0.8 to 2.2 cm/GW depending of sample composition, indicating its influences on the nonlinearity.

This paper reports the synthesis and characterization of ternary CdTe:Zn2+ quantum dots (QDs) passivated with reduced L-glutathione (GSH) dispersed in water. The synthesis was performed through a one-pot approach and their size-dependent optical properties were investigated through steady-state absorption and emission spectroscopies along with the evolving factor analysis/multivariate curve resolution alternating least squares (EFA/MCR-ALS) method. Our results show that the incorporation of Zn2+ ions in CdTe:Zn2+ QDs, during the synthesis time, decreases the CdTe:Zn2+ QDs predominant diameter in the ensemble and increases their size dispersion. In addition, fluorescence quantum yield measurements suggest a reduction in the number of surface defects in CdTe:Zn2+ QDs as compared with CdTe QDs, when both are produced from the same synthesis route.

We have interpreted the two-photon absorption spectrum of water-soluble copper indium sulfide (CIS) QDs with stoichiometry 0.18 (Cu), 0.42 (In), and 2 (S) and an average diameter of approximately 2.6 nm. For that, we employed the wavelength-tunable femtosecond Z-scan technique and the parabolic effective-mass approximation model, in which the excitonic transition energies were phenomenologically corrected due to the stoichiometry of the nanocrystal. This model considers a conduction band and three valence sub-bands allowing excitonic transitions via centrosymmetric (Δl = ±1, where l is the angular momentum of the absorbing state) and non-centrosymmetric (Δl = 0) channels. In such case, this became relevant because the CIS QDs with chalcopyrite crystalline structure is a non-centrosymmetric semiconductor. Thus, our experimental results pointed out two 2 PA allowed bands located at 715 nm (2hv = 3.47 eV) and 625 nm (2hv = 3.97 eV) with cross sections of (6.3 ± 1.0) x 102 GM and (4.5 ± 0.7) x 102 GM, respectively. According to the theoretical model, these 2 PA bands can be ascribed to the 1P1/2(h3) → 1S3/2(e) (lower energy band) and 1P1/2(hheavy) → 1S3/2(e) (90%)/(10%)1P1/2(hsplit-off) → 1P3/2(e) (higher energy band) excitonic transitions. A good agreement (magnitude and spectral position) between the experimental and theoretical data were obtained. However, our experimental data suggest that the higher-energy 2 PA band may have other contributions due to the mixing between the heavy- and the light-hole bands, which the effective mass model does not take into consideration.

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.

Two-photon absorption (2PA) spectroscopy is a powerful technique to investigate and understand, at the molecular level, the relationship between the molecular structure and electronic and optical properties of novel materials. Because of its remarkable features, such as the advantageous excitation in the near-infrared region and the high spatial localization of excitation, 2PA has been the target of several studies in distinct research fields, spanning from biology to physics. In this chapter, we describe the potential of the 2PA spectroscopy to investigate organic materials. For that, we initially present a brief introduction to the 2PA process. After that, we describe the fundamentals of 2PA within the electric dipole approximation. Subsequently, we present two experimental techniques widely used to determine the magnitude of the 2PA cross section in different materials, based on absorption and fluorescence mechanisms. As follows, we describe how to combine these techniques and the 2PA theory to obtain information on promising molecular designs that can be used to improve the nonlinear optical response and decrease the irradiance threshold necessary to generate a specific optical effect. To emphasize this important aspect, we present experimental results on distinct molecular structures. Finally, we present 2PA spectroscopy with polarization control and its potential for identifying the nature of the excited states and molecular structure of randomly oriented chromophores.

In this present paper, we investigate the relationship between the dynamic first-order hyperpolarizability (DFH, or βHRS) of a triarylamine core bearing two 3,3′-bis(trifluoromethyl)phenyl arms and the nature of a third group containing distinct electron-withdrawing strength (H < CN < CHO < NO2 < Cyet < Vin). For that, we have combined hyper-Rayleigh scattering (HRS) experiments with picosecond pulse train at 1064 nm and quantum chemical calculations at the density functional theory (DFT) level. The βHRS values exhibited pronounced enhancement from 56 × 10–30 cm5/esu (EWG = CN) up to ∼400 × 10–30 cm5/esu (EWG = Vin) due to the increase in the degree of donor–acceptor charge transfer concomitant with the intensification of the resonance enhancement effect observed when the scattered photon (2ω = 532 nm) approaches, in energy, the lowest energy band of chromophores. Furthermore, our experimental results suggest that the CF3 group has a significant effect on the βHRS, since we observed a considerable increas...

We have investigated the molecular structure and two-photon absorption (2PA) properties relationship of two push–pull poly(fluorene) derivatives containing benzoselenadiazole and benzothiadiazole units. For that, we have used the femtosecond wavelength-tunable Z-scan technique with a low repetition rate (1 kHz) and an energy per pulse on the order of nJ. Our results show that both 2PA spectra present a strong 2PA (around 600 GM (1 GM = 1 × 10−50 cm4·s·photon−1)) band at around 720 nm (transition energy 3.45 eV) ascribed to the strongly 2PA-allowed 1Ag-like → mAg-like transition, characteristic of poly(fluorene) derivatives. Another 2PA band related to the intramolecular charge transfer was also observed at around 900 nm (transition energy 2.75 eV). In both 2PA bands, we found higher 2PA cross-section values for the poly(fluorene) containing benzothiadiazole unit. This outcome was explained through the higher charge redistribution at the excited state caused by the benzothiadiazole group as compared to the benzoselenadiazole and confirmed by means of solvatochromic Stokes shift measurements. To shed more light on these results, we employed the sum-over-states approach within the two-energy level model to estimate the maximum permanent dipole moment change related to the intramolecular charge transfer transition.

We report here on the direct observation of distinct two-photon transition channels in glutathione-capped (GSH) CdTe quantum dots (QDs) in a very strong confinement regime. CdTe-GSH QDs with different average diameters (2.5, 3.0, and 3.3 nm) were synthesized through the one-pot method and their two-photon absorption (2PA) spectrum determined by a femtosecond wavelength-tunable Z-scan. Our results show that the two lower-energy one-photon-allowed excitonic transitions, 1S3/2(h) → 1S(e) and 2S3/2(h) → 1S(e), are also accessed via 2PA. These results were ascribed to the relaxation of the parity selection rules due to the noncentrosymmetric structure of the CdTe QDs (zinc-blended structure), whose magnitude are determined by surface defects and structural irregularities present in CdTe-GSH QDs, in the strong confinement regime.

Herein, we report on the two-absorption cross-section spectrum of trans-Pt(PBu3)2 (C≡C-C6H4-C≡C-C6H5)2 (PE2) platinum acetylide complex employing the femtosecond wavelength-tunable Z-scan technique. The PE2 complex can be visualized as two branches containing two phenylacetylene units, each one linked by a platinum center, completely transparent in the visible region. Because of this structure, large delocalization of π-electrons allied to the strong intramolecular interaction between the branches is expected. The 2PA absorption spectrum was measured using the femtosecond wavelength-tunable Z-scan technique with low repetition rate (1 kHz), in order to obtain the 2PA spectrum without excited-state contributions. Our results reveal that PE2 in dichloromethane solution presents two 2PA allowed bands located at 570 and 710 nm, with cross section of about 320 and 45 GM, respectively. The first one is related to the strong intramolecular interaction between the molecule's branches due to the presence of platinum atom, while the second one is associated with the breaking of symmetry of the chromophore in solution due, most probably to a large twisting angle of the ligand's phenyl rings relative to the Pt core.

In this present work, we investigated the singlet excited state absorption (ESA) spectrum and intersystem crossing dynamics of gadolinium phthalocyanine (GdPc) in toluene. For that, we employed the femtosecond wavelength-tunable Z-scan and picosecond Pulse Train Fluorescence (PTF) techniques to determine, respectively, the singlet ESA cross-section on a wide spectral range (from 460 up to 740 nm) and the intersystem crossing time (singlet–triplet transition). We observed that the ESA spectrum presents distinct absorption behaviors, i.e., saturable (SA) and reverse saturable absorption (RSA). We have also been able to identify regions in which the excited state absorption cross-section has the same magnitude as the ground state one (at 600 and 720 nm). The RSA effect was observed for wavelengths shorter than 600 nm and longer than 720 nm, while SA occurs in the Q-band region, located between 600 and 720 nm. To describe the main singlet–singlet transitions, we measured the fluorescence decay time and employed a rate equation model considering a three-energy-level-diagram. Ratios between excited and ground state absorption cross-section from 0.4 to 4 were observed along the ESA spectrum. From these results, we calculated the transition dipole moment between the excited states for the main electronic transitions of GdPc. To obtain the intersystem crossing time, we incorporated an additional level in our model and used the PTF technique to probe the population transfer to the triplet state. Our results pointed out that the intersystem crossing time is higher than 300 ns, which corresponds to a maximum triplet quantum yield of 1.5%.

We report a quantitative wavelength-resolved analysis (460–600 nm) of the two-photon absorption (2PA) cross-section of water-soluble MPA-capped ZnS quantum dots (QDs). For that, we employed the open-aperture Z-scan technique using an amplified femtosecond laser system operating at low repetition rate (1 kHz). MPA-capped ZnS QDs with size distribution centered at ca. 3.8 nm were synthesized using the one-step aqueous procedure. The molar absorptivity of the lowest energy one-photon transition from ZnS QDs (1S3/2(h) → 1S(e)) was estimated in ∼6.5 × 104 M–1 cm–1. Nonlinear spectroscopic data showed that ZnS QDs present 2PA in the region between 4.15 and 4.35 eV (2hν) due to the 1S1/2(h1) → 1P3/2(e) low energy transition. Furthermore, two 2PA bands centered at 4.68 and 5.25 eV (2hν), associated with higher energy excitonic transitions, were also observed. The 2PA cross-section values along the entire spectral region measured (2hν = 4.15 to 5.4 eV) are in the order of 102 Goeppert–Mayer units. By means of a th...

Herein, we report on the theoretical-experimental analysis of the two-photon absorption (TPA) and two-photon circular-linear dichroism (TPCLD) spectra of a highly conjugated, rigid, and centrosymmetric molecule in solution, that is, perylene/CH2Cl2. We show how a three-energy-level diagram, under the sum-over-essential states approach, assists in the determination of the magnitude of transition electric dipole moments and the angle between them for the main TPA transitions. We demonstrate the potential of TPCLD to reveal the symmetry of excited states and the angles between their transition electric dipole moments and that of the ground state. By means of TPCLD, we explain how the overwhelming contribution of certain TPA transitions can mask important spectral features in regions where the transition electric dipole moments are perpendicular. TPCLD is expected to enhance the understanding of the photophysical properties of materials that are not accessible using conventional linear and two-photon spectroscopy. TPA and TPCLD measurements were performed employing the open-aperture Z-scan technique using an amplified femtosecond system. Time-dependent density functional theory (TD-DFT) calculations were carried out using response theory at the B3LYP level with the aug-cc-pVDZ basis set. Solvent effects were included through the polarizable continuum model (PCM).

We investigate the excited state intramolecular proton transfer dynamic for a salophen derivative chromophore by using white-light continuum femtosecond pump-probe and quantum chemical calculations within the DFT framework.

This paper report on the excited-state (ESA) and two-photon absorption (2PA) features of two novel salicylidene compounds: N,N′-bis(salicylidene)-1,2-phenylenediamine (salophen) and its Zn(II) coordination compound ([Zn(salophen) (OH2)]). The molecular structure of salophen is a tetradentated ligand with iminic and phenolic bonding sites, allowing the coordination of metal ions such as zinc(II) forming [Zn(salophen) (OH2)]. According to our data, the Zn(II) coordination complex modifies the ESA and 2PA spectrum of the salophen ligand, increasing significantly its hyperpolarizability and improving its optical properties due to the increase of the planarity and rigidity of the ligand framework. In order to obtain more information about optical properties of these molecules, theoretical calculations were performed at the DFT/TD-DFT level using aug-cc-pVDZ/CAM-B3LYP. Our results suggest that the molecular geometries of the ligand, corresponding to S0 and S1 states, are quite similar. However, the coordination...

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

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.

In this Letter, we explored the use of polarized two-photon absorption (2PA) spectroscopy, which brings additional information when compared to methods that do not use polarization control, to investigate the electronic and molecular structure of two chromophores (FD43 and FD48) based on phenylacetylene moieties. The results were analyzed using quantum chemical calculations of the two-photon transition strengths for circularly and linearly polarized light, provided by the response function formalism. On the basis of these data, it was possible to distinguish and identify the excited electronic states responsible for the lowest-energy 2PA-allowed band in both chromophores. By modeling the 2PA circular-linear dichroism, within the sum-over-essential states approach, we obtained the relative orientation between the dipole moments that are associated with the molecular structure of the chromophores in solution. This result allowed to correlate the V-shape structure of the FD48 chromophore and the quantum-interference-modulated 2PA strength.

This paper reports on the static and dynamic first-order hyperpolarizabilities of a class of push-pull octupolar triarylamine derivatives dissolved in toluene. We have combined hyper-Rayleigh scattering experiment and the coupled perturbed Hartree-Fock method implemented at the Density Functional Theory (DFT) level of theory to determine the static and dynamic (at 1064 nm) first-order hyperpolarizability (βHRS) of nine triarylamine derivatives with distinct electron-withdrawing groups. In four of these derivatives, an azoaromatic unit is inserted and a pronounceable increase of the first-order hyperpolarizability is reported. Based on the theoretical results, the dipolar/octupolar character of the derivatives is determined. By using a polarizable continuum model in combination with the DFT calculations, it was found that although solvated in an aprotic and low dielectric constant solvent, due to solvent-induced polarization and the frequency dispersion effect, the environment substantially affects the first-order hyperpolarizability of all derivatives investigated. This statement is supported due to the solvent effects to be essential for the better agreement between theoretical results and experimental data concerning the dynamic first-order hyperpolarizability of the derivatives. The first-order hyperpolarizability of the derivatives was also modeled using the two- and three-level models, where the relationship between static and dynamic first hyperpolarizabilities is given by a frequency dispersion model. Using this approach, it was verified that the dynamic first hyperpolarizability of the derivatives is satisfactorily reproduced by the two-level model and that, in the case of the derivatives with an azoaromatic unit, the use of a damped few-level model is essential for, considering also the molecular size of such derivatives, a good quantitative agreement between theoretical results and experimental data to be observed.

This work investigates the two-photon absorption (2PA) spectrum of all-trans retinoic acid (ATRA) in DMSO solution, employing the wavelength-tunable Z-scan and white-light pump-probe techniques with femtosecond pulses. Our results showed that ATRA presents two 2PA allowed bands at 280 nm (2hν = 560 nm) and 365 nm (2hν = 730 nm) with 2PA cross-section values of 34 GM and 40 GM, respectively. The 2PA band at 280 nm was ascribed to the transition from ground to high energy excited states with contribution from the real intermediate excited state (11Bu+-like). The 2PA band at 365 nm was attributed to an overlap of 11Bu+-like and 21Ag−-like excited states, which are essential to describe the photochemical processes that this class of organic materials play in nature. Through solvatochromic measurements and by using the two-energy level approach, we found that the 11Bu+-like and 21Ag−-like states contribute, respectively, 48% and 52% of the lowest energy 2PA band of ATRA in DMSO solution. From femtosecond transient spectroscopy we verified that when ATRA is excited at 775 nm (2PA excitation) its excited state absorption (ESA) spectrum presents a red-shift of ∼5.5 nm in comparison to the same spectrum excited at 387.5 nm (1PA excitation), corroborating the interpretation about the 2PA spectrum for the ATRA in DMSO.

This article reports on a comprehensive study of the two-photon absorption (2PA) properties of six novel push-pull octupolar triarylamine compounds as a function of the nature of the electron-withdrawing groups. These compounds present an octupolar structure consisting of a triarylamine core bearing two 3,3′-bis(trifluoromethyl)phenyl arms and a third group with varying electron-withdrawing strength (H < CN < CHO < NO2 < Cyet < Vin). The 2PA cross-sections, measured by using the femtosecond open-aperture Z-scan technique, showed significant enhancement from 45 up to 125 GM for the lowest energy band and from 95 up to 270 GM for the highest energy band. The results were elucidated based on the large changes in the transition and permanent dipole moments and in terms of (i) EWG strength, (ii) degree of donor-acceptor charge transfer and (iii) electronic coupling between the arms. The 2PA results were eventually supported and confronted with theoretical DFT calculations of the two-photon transition oscillator strengths.

In the present study, we report the synthesis of glutathione (GSH) capped CdTe quantum dots (QDs) using the one-pot approach as well as their optical properties. These QDs were used as a probe for a detailed quantitative correlation between spectroscopic data and QDs size dispersion. We have developed a spectroscopic method to determine the size dispersion of QDs in solution based on the fluorescence spectroscopy and the fluorescence quantum yields. Our results demonstrate that the one-pot approach produces GSH-capped CdTe QDs of narrow size dispersion, as inferred by the sharp line width (full width at half maximum) of the fluorescence signal (from 153 meV to 163 meV), as revealed by our spectroscopy method. We observed that the GSH-capped CdTe QDs cause an increase in fluorescence quantum yield from 11% to 30% concomitantly with an increase in lifetime decay from 38 to 50 ns during the course of synthesis (from 15 min to 120 min), indicating an increase in the average size of the QDs. Finally, we have used the evolving factor analysis together with the multivariate curve resolution-alternating least squares method to corroborate our results, and we found a good agreement between both methods with the advantage that in our method, we were able to obtain size dispersion rather than just the mean QD size.

This paper reports on the strong two-photon absorption (2PA) of the trans-Pt(PBu3)2(C≡C–C6H4–C≡C–C6H4–C≡C–C6H5)2 (PE3) platinum acetylide complex dissolved in dichloromethane in the visible and near-infrared region. The 2PA spectrum was measured though the open-aperture Z-scan technique using an amplified femtosecond laser system (150 fs) operating at low repetition rate (1 kHz). Since PEs present short intersystem crossing time (ps) and long phosphorescence time (μs), the 2PA cross-section obtained from the Z-scan technique may have contribution from the triplet states. However, we show by a rate equations model and pump–probe experiments that the rate of population transferred to the triplet state via 2PA, employing a 150 fs laser, and low repetition is negligible (

We studied the photocatalysis of Rhodamine B assisted by TiO2 achieved by fs-pulses excitation at 800 nm. Nonlinear spectroscopy measurements were performed to in the samples to understand the mechanism behind the observed photocatalysis.

In this report we investigate the two-photon absorption circular-linear dichroism (2PA-CLD) of two chiral molecules based on phenylacetylene moieties employing the Z-scan technique with polarization control

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.

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.

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.

In this report, we study the effect of Electron Withdrawing substituents (EWG) on the two-photon absorption properties of a novel class of push-pull triarylamine compounds containing trifluoromethyl (CF3).

The aim of this report was investigate the conformational change effect of Poly(3,6 phenanthrene)s induced by the action of solvent on their two-photon absorption (2PA) properties. Such properties were investigated employing the wavelength-tunable femtosecond Z-scan technique.

International audience; This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a π-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p25) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.

This work demonstrates that the detuning of the fs-laser spectrum from the two-photon absorption band of organic materials can be used to reach further control of the two-photon absorption by pulse spectral phase manipulation. We investigate the coherent control of the two-photon absorption in imidazole–thiophene core compounds presenting distinct two-photon absorption spectra. The coherent control, performed using pulse phase shaping and genetic algorithm, exhibited different growth rates for each sample. Such distinct trends were explained by calculating the two-photon absorption probability considering the intrapulse interference mechanism, taking into account the two-photon absorption spectrum of the samples. Our results indicate that tuning the relative position between the nonlinear absorption and the pulse spectrum can be used as a novel strategy to optimize the two-photon absorption in broadband molecular systems.

Carotenoids are biosynthetic organic pigments that constitute an important class of one-dimensional π-conjugated organic molecules with enormous potential for application in biophotonic devices. In this context, we studied the degenerate two-photon absorption (2PA) cross-section spectra of two carotenoid compounds (β-carotene and β-apo-8′-carotenal) employing the conventional and white-light-continuum Z-scan techniques and quantum chemistry calculations. Because carotenoids coexist at room temperature as a mixture of isomers, the 2PA spectra reported here are due to samples containing a distribution of isomers, presenting distinct conjugation length and conformation. We show that these compounds present a defined structure on the 2PA spectra, that peaks at 650 nm with an absorption cross-section of approximately 5000 GM, for both compounds. In addition, we observed a 2PA band at 990 nm for β-apo-8′-carotenal, which was attributed to a overlapping of 11Bu+-like and 21Ag–-like states, which are strongly one...