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1.
Spectrochim Acta A Mol Biomol Spectrosc ; 317: 124409, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-38733912

RESUMO

Rhodamines constitute a class of dyes extensively investigated and applied in various contexts, primarily attributed to their high luminescence quantum yield. This study delves into the impact of aggregation on the thermal and optical properties of Rhodamine 6G (R-6G) solutions in distilled water. Examined properties encompass thermal diffusivity (D), temperature coefficient of the refractive index (dn/dT), fluorescence quantum efficiency (η), and energy transfer (ET). These parameters were assessed through thermal lens (TL) and conventional absorption and emission spectroscopic techniques. The dimerization of R-6G solutions was revisited, revealing that an increase in R-6G concentration alters the features of absorption and emission spectra due to dimer formation, resulting in unexpected behavior of η. Consequently, we introduce a novel model for the fraction of absorbed energy converted into heat (φ), which accounts for emissions from both monomers and dimers. Employing this model, we investigate and discuss the concentration-dependent behaviors of η for monomers (ηm) and dimers (ηd). Notably, our findings demonstrate that ηm values necessitate ηd = 0.2, a relatively substantial value that cannot be disregarded. Additionally, applying the Förster theory for dipole-dipole electric ET, we calculate microparameters for ET between monomers (CDD) and monomer-dimer (CDA). Critical ranges for ET in each case are quantified. Microparameter analysis indicates that ET between monomer-monomer and monomer-dimer species of R-6G dissolved in distilled water holds significance, particularly in determining ηm. These results bear significance, especially in scenarios involving high dye concentrations. While applicable to R-6G in water, similar assessments in other media featuring aggregates are encouraged.

2.
Sci Rep ; 14(1): 5595, 2024 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-38454075

RESUMO

The interaction of localized light with matter generates optical electrostriction within dielectric fluids, leading to a discernible change in the refractive index of the medium according to the excitation's light profile. This optical force holds critical significance in optical manipulation and plays a fundamental role in numerous photonic applications. In this study, we demonstrate the applicability of the pump-probe, photo-induced lensing (PIL) method to investigate optical electrostriction in various dielectric liquids. Notably, the thermal and nonlinear effects are observed to be temporally decoupled from the electrostriction effects, facilitating isolated observation of the latter. Our findings provide a comprehensive explanation of optical forces in the context of the recently introduced microscopic Ampère electromagnetic formalism, which is grounded in the dipolar approximation of electromagnetic sources within matter and characterizes electrostriction as an electromagnetic-induced stress within the medium. Here, the optical force density is re-obtained through a new Lagrangian approach.

3.
Photoacoustics ; 29: 100445, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36632605

RESUMO

We present semi-analytical solutions describing the spatiotemporal distributions of temperature and pressure inside low-absorbing dielectrics excited by tightly focused laser beams. These solutions are compared to measurements in water associated with variations of the local refractive index due to acoustic waves generated by electrostriction, heat deposition, and the Kerr effect at different temperatures. The experimental results exhibited an excellent agreement with the modeling predictions, with electrostriction being the dominant transient effect in the acoustic wave generation. Measurements at 4 . 0 ∘ C show that the thermoelastic contribution to the optical signal is significantly reduced due to the low thermal expansion coefficient of water at this temperature.

4.
Light Sci Appl ; 11(1): 103, 2022 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-35443703

RESUMO

Precise control over light-matter interactions is critical for many optical manipulation and material characterization methodologies, further playing a paramount role in a host of nanotechnology applications. Nonetheless, the fundamental aspects of interactions between electromagnetic fields and matter have yet to be established unequivocally in terms of an electromagnetic momentum density. Here, we use tightly focused pulsed laser beams to detect bulk and boundary optical forces in a dielectric fluid. From the optical convoluted signal, we decouple thermal and nonlinear optical effects from the radiation forces using a theoretical interpretation based on the Microscopic Ampère force density. It is shown, for the first time, that the time-dependent pressure distribution within the fluid chiefly originates from the electrostriction effects. Our results shed light on the contribution of optical forces to the surface displacements observed at the dielectric air-water interfaces, thus shedding light on the long-standing controversy surrounding the basic definition of electromagnetic momentum density in matter.

5.
Spectrochim Acta A Mol Biomol Spectrosc ; 145: 125-129, 2015 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-25770935

RESUMO

Assessment of photochemical stability is essential for evaluating quality and the shelf life of vegetable oils, which are very important aspects of marketing and human health. Most of conventional methods used to investigate oxidative stability requires long time experimental procedures with high consumption of chemical inputs for the preparation or extraction of sample compounds. In this work we propose a time-resolved thermal lens method to analyze photostability of edible oils by quantitative measurement of photoreaction cross-section. An all-numerical routine is employed to solve a complex theoretical problem involving photochemical reaction, thermal lens effect, and mass diffusion during local laser excitation. The photostability of pure oil and oils with natural and synthetic antioxidants is investigated. The thermal lens results are compared with those obtained by conventional methods, and a complete set of physical properties of the samples is presented.


Assuntos
Lentes , Luz , Análise Espectral/métodos , Temperatura , Oxirredução , Processamento de Sinais Assistido por Computador , Óleo de Soja
6.
J Phys Chem A ; 118(31): 5983-8, 2014 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-25017719

RESUMO

Photophysics processes are ubiquitous in nature and difficult to be quantitatively characterized by conventional spectroscopy. Alternatively, pump-probe methods have been widely applied to study these complex processes. In this context, the thermal lens technique is a precise spectroscopic tool for material characterization and presents a wide range of applications in chemical analysis. Here, we present an all numerical approach to analyze the dynamics of photophysics processes and to identify the role of individual contributions of photoreaction and mass diffusion in the thermal lens experiments. The results are essential for a proper understanding of the dominant physical mechanisms in laser-induced photodegradation, which allow precise data analysis of the effects in photosensitive fluids.

7.
Artigo em Inglês | MEDLINE | ID: mdl-24374885

RESUMO

In this work, the phase-resolved photoacoustic method was applied to provide specific information on the chemical assignments of paracetamol in the near-infrared region. Two broad bands, centered at 1370 and 1130 nm, were well-resolved using this method, making it possible to assign the peaks centered at 1398, 1355 and 1295 nm to a C-H combination from a CH3 structure and the peak at 1305 nm to a C-H combination from the aromatic ring. This information represents a new finding in chemical studies regarding this medicament.


Assuntos
Acetaminofen/química , Técnicas Fotoacústicas/métodos , Absorção , Espectroscopia de Infravermelho com Transformada de Fourier , Espectroscopia de Luz Próxima ao Infravermelho
8.
Opt Lett ; 38(4): 422-4, 2013 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-23455089

RESUMO

We report a theoretical model and experimental results for laser-induced lensing in solids. The model distinguishes and quantifies the contributions from population and thermal effects. Laser-induced lensing in ytterbium-doped fluorozirconate glass ZBLAN:Yb(3+) is measured, and the thermal and optical properties obtained from analyzing the data with the proposed model agree well with published values. Photothermal techniques are used extensively for the investigation of laser and laser-cooling materials, and the model developed here enables the interpretation of convoluted laser-induced lensing signals that have contributions from different sources.

9.
J Phys Chem B ; 117(6): 1932-7, 2013 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-23374106

RESUMO

Eosin Y is known to be a powerful probe of biological molecules and an efficient photosensitizing agent for the production of singlet molecular oxygen. Under continuous laser excitation, degradation through photobleaching is observed in aqueous solutions of eosin Y; this process is driven by the production of singlet oxygen. Optical bleaching in aqueous solutions is known to yield anomalous thermal lens transient signals, which can be evaluated by modeling the relaxation processes that give rise to the generation of heat in the solution. A model describing photobleaching in the thermal lens transient signal is derived and is applied to investigate eosin Y in aqueous solutions at different temperatures. Using this model, quantitative information regarding the molecular diffusion rate, optical bleaching, and fluorescence quantum efficiency is obtained.


Assuntos
Amarelo de Eosina-(YS)/química , Fotodegradação , Cinética , Modelos Moleculares , Oxigênio Singlete/química , Espectrofotometria Ultravioleta , Temperatura , Água/química
10.
J Phys Chem B ; 115(30): 9417-20, 2011 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-21699235

RESUMO

A dual-wavelength on/off-excitation thermal lens technique was used to identify and quantify a laser-induced chemical reaction in ionic aqueous solutions of Fe(II)-TPTZ. On/off modeling was used to fit the TL experimental data, which provided the primary effect generated during laser-excitation. The addition of HCl in the solutions reduced the activation barrier; this behavior followed the Arrhenius correlation. The nature of the photo-oxidation of Fe(II)-TPTZ complex is discussed. The results suggest that this technique may contribute to the understanding of the dynamics of complex reactions, which may lead to a more precise determination of the physicochemical properties involved in a photochemical reaction.

11.
J Chem Phys ; 134(12): 124503, 2011 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-21456672

RESUMO

In this work we present a comprehensive study of the spectroscopic and thermo-optical properties of a set of samples with composition xNd(2)O(3)-(5-x)Y(2)O(3-)40CaO-55B(2)O(3) (0 ≤ x ≤ 1.0 mol%). Their fluorescence quantum efficiency (η) values were determined using the thermal lens technique and the dependence on the ionic concentration was analyzed in terms of energy transfer processes, based on the Förster-Dexter model of multipolar ion-ion interactions. A maximum η = 0.54 was found to be substantially higher than for yttrium aluminoborate crystals and glasses with comparable Nd(3+) content. As for the thermo-optical properties of yttrium calcium borate, they are comparable to other well-known laser glasses. The obtained energy transfer microparameters and the weak dependence of η on the Nd(3+) concentration with a high optimum Nd(3+) concentration put this system as a strong candidate for photonics applications.

12.
Opt Express ; 19(5): 4047-58, 2011 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-21369233

RESUMO

We report a theoretical model and experimental results for laser-induced local heating in liquids, and propose a method to detect and quantify the contributions of photochemical and Soret effects in several different situations. The time-dependent thermal and mass diffusion equations in the presence and absence of laser excitation are solved. The two effects can produce similar transients for the laser-on refractive index gradient, but very different laser-off behavior. The Soret effect, also called thermal diffusion, and photochemical reaction contributions in photochemically reacting aqueous Cr(VI)-diphenylcarbazide, Eosin Y, and Eosin Y-doped micellar solutions, are decoupled in this work. The extensive use of lasers in various optical techniques suggests that the results may have significance extending from physical-chemical to biological applications.


Assuntos
Calefação/métodos , Lasers , Modelos Químicos , Fotoquímica/métodos , Soluções/química , Soluções/efeitos da radiação , Simulação por Computador
13.
J Chem Phys ; 133(3): 034507, 2010 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-20649337

RESUMO

Pump and thermally induced color tunabilities were demonstrated in Yb(3+)/Tm(3+) codoped low silica calcium aluminosilicate (LSCAS) glass under anti-Stokes excitation at 1.064 microm. The effects of pump intensity and sample's temperature on the upconversion emissions and mainly on the color tunabilities (from 800 to 480 nm) were investigated. The results revealed a 20- and a threefold reductions at 800/480 nm ratio as, respectively, the pump intensity and sample's temperature were increased from 27 to 700 kW/cm(2) and from 296 to 577 K. These behaviors with pump intensity and temperature (a strong increase of the 480 nm emission in comparison with the 800 nm one) were attributed to the several efficient processes occurring in the LSCAS system (Yb(3+)-->Tm(3+) energy-transfer processes, easy saturations of the Yb(3+) and Tm(3+) excited states, and radiative emissions). Besides these assigns, the temperature dependence is mainly assigned to the temperature-dependent effective absorption cross section of the ytterbium sensitizer through the so-called multiphonon-assisted anti-Stokes excitation process. Theoretical analyses and fits of the experimental data provided quantitative information.

14.
Opt Express ; 16(26): 21248-55, 2008 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-19104555

RESUMO

In this work the time resolved thermal lens method is combined with interferometric technique, the thermal relaxation calorimetry, photoluminescence and lifetime measurements to determine the thermo physical properties of Nd(2)O(3) doped sodium zincborate glass as a function of temperature up to the glass transition region. Thermal diffusivity, thermal conductivity, fluorescence quantum efficiency, linear thermal expansion coefficient and thermal coefficient of electronic polarizability were determined. In conclusion, the results showed the ability of thermal lens and interferometric methods to perform measurements very close to the phase transition region. These techniques provide absolute values for the measured physical quantities and are advantageous when low scan rates are required.

15.
Phys Rev Lett ; 100(2): 027402, 2008 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-18232921

RESUMO

This Letter reports the formation of Ti3+ in OH- free aluminosilicate glass melted under vacuum condition, with a very long lifetime (170 micros) and broad emission band shifted towards the visible region. This lifetime value was attributed to the trapping of the excited electrons by the glass defects and detrapping by thermal energy, and it is 2 orders of magnitude higher than those published for Ti3+ doped materials. Our results suggest that this glass is a promising system to overcome the challenge of extending the spectral range of traditional tunable solid state lasers towards the visible region.

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