Electron capture and emission by the Ti acceptor level in GaP

Previously reported results on deep level optical spectroscopy, optical absorption, deep level transient spectroscopy, photoluminescence excitation, and time resolved photoluminescence are reviewed and discussed in order to know which are the mechanisms involved in electron capture and emission of the Ti acceptor level in GaP. First, the analysis indicates that the 3T1(F) crystal¿field excited state is not in resonance with the conduction band states. Second, it is shown that both the 3T2 and 3T1(F) excited states do not play any significant role in the process of electron emission and capture.

Silicon nanocluster sensitization of erbium ions under low-energy optical excitation

The sensitizing action of amorphous silicon nanoclusters on erbium ions in thin silica films has been studied under low-energy (long wavelength) optical excitation. Profound differences in fast visible and infrared emission dynamics have been found with respect to the high-energy (shortwavelength) case. These findings point out to a strong dependence of the energy transfer process on the optical excitation energy. Total inhibition of energy transfer to erbium states higher than thefirst excited state (4I13/2) has been demonstrated for excitation energy below 1.82 eV (excitation wavelength longer than 680 nm). Direct excitation of erbium ions to the first excited state (4I13/2)has been confirmed to be the dominant energy transfer mechanism over the whole spectral range of optical excitation used (540 nm¿680 nm).

Growth, optical characterization, and laser operation of a stoichiometric crystal KYb(WO4)(2)

We present our recent achievements in the growing and optical characterization of KYb(WO4)2 (hereafter KYbW) crystals and demonstrate laser operation in this stoichiometric material. Single crystals of KYbW with optimal crystalline quality have been grown by the top-seeded-solution growth slow-cooling method. The optical anisotropy of this monoclinic crystal has been characterized, locating the tensor of the optical indicatrix and measuring the dispersion of the principal values of the refractive indices as well as the thermo-optic coefficients. Sellmeier equations have been constructed valid in the visible and near-IR spectral range. Raman scattering has been used to determine the phonon energies of KYbW and a simple physical model is applied for classification of the lattice vibration modes. Spectroscopic studies (absorption and emission measurements at room and low temperature) have been carried out in the spectral region near 1 µm characteristic for the ytterbium transition. Energy positions of the Stark sublevels of the ground and the excited state manifolds have been determined and the vibronic substructure has been identified. The intrinsic lifetime of the upper laser level has been measured taking care to suppress the effect of reabsorption and the intrinsic quantum efficiency has been estimated. Lasing has been demonstrated near 1074 nm with 41% slope efficiency at room temperature using a 0.5 mm thin plate of KYbW. This laser material holds great promise for diode pumped high-power lasers, thin disk and waveguide designs as well as for ultrashort (ps/fs) pulse laser systems.

O comportamento Fotoquímico dos Complexos Pentaaminas de Rutênio(II) com Ligantes π Insaturados

A general overview on the photochemical behaviour of [Ru(NH3)5L]2+ complexes (where L is a p ligand) is presented. The proposed mechanisms and techniques employed for the study of these reactions are discussed. Emphasis is made on the mechanisms that allow the identification of the reactive excited state of the [Ru(NH3)5py]2+ complex.

Quimiluminescência orgânica: alguns experimentos de demonstração para a sala de aula

The generation of "cold light", visible to the human eye, by chemical reactions has attracted the attention of the scientific community since the beginning of this century. Besides the academic interest in the elucidation of the mechanisms of excited state formations, many chemiluminescence reactions have found widespread analytical applications. Moreover, the phenomenon of chemiluminescence can also be used as a tool in undergraduate and college teaching. In this article, we describe several known chemiluminescence demonstrations, which are suitable for school teaching. The main objective of this work is to produce didactic material in Portuguese to stimulate Brazilian secondary and high school teachers to use these experiments in the classroom. The demonstrations include singlet oxygen emission, the luminol reaction, oscillating chemiluminescence and the peroxyoxalate reaction.

Utilização de endoperóxidos de derivados de naftaleno como fontes químicas de oxigênio singlete em sistemas biológicos

Molecular oxygen, in the first excited state (singlet oxygen, ¹O2), has a substantial reactivity towards electron-rich organic molecules, such as biological targets, including unsaturated fatty acids, proteins, RNA and DNA. Considering the complexity of biological systems and the great variety of reactive species generated by photochemistry, efforts have been devoted to develop suitable ¹O2 generators based on the thermolysis of water soluble naphthalene endoperoxides. These compounds are chemically inert and have been employed as versatile sources of ¹O2. The synthesis is based on structural modifications in position 1,4 of dimethylnaphtalene, grafting hydrophilic substituents. The correspondent endoperoxide can be generated using photochemical method, or molybdate-catalyzed disproportionation of hydrogen peroxide.

Quimiluminescência de peróxidos orgânicos: geração de estados eletronicamente excitados na decomposição de 1,2-dioxetanos

In this review article, we give a general introduction on the mechanisms involved in organic chemiluminescence, where three basic models for excited state formation are presented. The chemiluminescence properties of 1,2-dioxetanes - four membered ring peroxides - are briefly outlined in the second part. In the main part, the mechanisms involved in the decomposition of 1,2-dioxetanes and analogous peroxides are discussed: (i) the unimolecular decomposition of 1,2-dioxetanes; (ii) the electron transfer catalyzed decomposition of peroxides by an intermolecular CIEEL (Chemically Initiated Electron Exchange Luminescence) mechanism; (iii) 1,2-dioxetane decomposition catalyzed by an intramolecular electron transfer mechanism (intramolecular CIEEL). Special emphasis is given to the latter subject, where recent examples with potential analytical applications are presented.

A reatividade do estado excitado triplete de 1,3-indanodiona em benzeno

Rate constants for the quenching of 1,3-indandione (1) triplet by olefins and by hydrogen and electron donors were obtained employing the laser flash photolysis technique in benzene solution. These rate constants ranged from 2.5x10(5) Lmol-1s-1 (for 2-propanol) to 5.9x10(9) Lmol-1s-1 (for DABCO). From the quenching rate constants by 1,3-cyclohexadiene, trans- and cis-stilbene a value between 49.3 and 52.4 kcal/mol was estimated for the energy of the triplet state of 1,3-indandione. The npi* character of this triplet state was evidenced by the quenching rate constants obtained when typical hydrogen donors were employed as quenchers. For 2-phenyl-1,3-indandione (2, R=phenyl) a fast Norrish type I reaction is operating which prevents the determination of kinetic and spectroscopic data of its triplet state.

I2: uma molécula didática

Iodine vapor is a very suitable substance to learn about molecular energy levels and transitions, and to introduce spectroscopic techniques. As a diatomic molecule its spectra are relatively simple and allow straightforward treatment of the data leading to the potential energy curves and to quantum mechanics concepts. The overtone bands, in the resonance Raman scattering, and the band progressions, in the electronic spectra, play an important role in the calculation of the Morse potential curves for the fundamental and excited electronic state. A weaker chemical bond in the electronic excited state, compared to the fundamental state, is evidenced by the increase in the equilibrium interatomic distance. The resonance Raman scattering of I2 is highlighted due to its importance for obtaining the anharmonicity constant in the fundamental electronic state.

Técnica de bombeio e prova para medidas de absorção de estado excitado e de emissão estimulada, em materiais sólidos dopados com íons terras raras

Rare earth ion doped solid state materials are the most important active media of near-infrared and visible lasers and other photonic devices. In these ions, the occurrence of Excited State Absorptions (ESA), from long lived electronic levels, is commonplace. Since ESA can deeply affect the efficiencies of the rare earth emissions, evaluation of these transitions cross sections is of greatest importance in predicting the potential applications of a given material. In this paper a detailed description of the pump-probe technique for ESA measurements is presented, with a review of several examples of applications in Nd3+, Tm3+ and Er3+ doped materials.

Estudo da reatividade do estado excitado triplete de 1,4-diaza-9-fluorenonas frente a doadores de hidrogênio e de elétron

The effect of the introduction of nitrogen atoms upon the triplet excited state reactivity of 1,4-diaza-9-fluorenone (1) and 1,4-diaza-9-benz[b]fluorenone (2), in acetonitrile, was investigated employing the nanosecond laser flash photolysis technique. The intersystem crossing quantum yield (Φces) for 1 and 2 was determined using 9-fluorenone as a secondary standard (Φces= 0.48, in acetonitrile) and for both diazafluorenones a value of Φces= 0.28 was found. Quenching rate constants ranged from 8.17x10(4) L mol-1 s-1 (2-propanol) to 1.02x10(10) L mol-1 s-1 (DABCO) for 1,4-diaza-9-fluorenone and from 6.95x10(5) L mol-1 s-1 (2-propanol) to 5.94x10(9) L mol-1 s-1 (DABCO) for 1,4-diaza-9-benz[b]fluorenone, depending if the quenching process involves energy, hydrogen or electron transfer. A comparison between quenching rate constants for both diazaflurenones and the parent compound, i.e. 9-fluorenone, a ketone with lowest triple state of ππ* configuration, lead to the conclusion that the reactive triplet excited state for 1,4-diaza-9-fluorenone and 1,4-diaza-9-benz[b]fluorenone has ππ* configuration.

Líquido iônico [bmim.PF6] como solvente: um meio conveniente para estudos por fotólise por pulso de laser

The spectroscopic behavior of thioxanthone and benzil (diphenylethanedione or dibenzoyl) in the ionic liquid [bmim.PF6] has been investigated employing the laser flash photolysis technique. Triplet-triplet absorption spectra for these carbonyl compounds in [bmim.PF6] are similar to those observed in organic solvents. The triplet lifetime for thioxanthone in desogygenated samples is very long (71 μs), whereas in oxygen-saturated solution is 500 ns, which indicates the low oxygen solubility in this solvent. For benzil, lifetimes of 10 μs in [bmim.PF6] and 3.8 μs in acetonitrile were obtained. The decay for triplet thioxanthone and benzil follows a clear first order kinetics in [bmim.PF6], from which one can conclude that triplet-triplet annihilation is not an important decay process in this solvent.

Luz: um raro produto de reação

The production of visible light by chemical reactions constitutes interesting and fascinating phenomena and several reaction mechanisms are discussed to rationalize excited state formation. Most efficient chemiluminescence reactions are thought to involve one or more electron transfer steps and chemiexcitation is believed to occur by radical annihilation. A brief introduction to the general principles of light production and the main known chemiexcitation mechanisms will be given here. Subsequently, recent results on the mechanistic elucidation of efficient chemiluminescence systems, as the peroxyoxalate reaction, the induced decomposition of phenoxy-substituted 1,2-dioxetanes and the catalyzed decomposition of new a-peroxylactones will be discussed.

Simulação Monte Carlo de mecanismo de transferência de energia de excitação eletrônica: modelo de Perrin para a supressão estática da luminescência

A software based in the Monte Carlo method has been developed aiming the teaching of the Perrin´s model for static luminescence quenching. This software allows the student to easily simulate the luminescence decays of emissive molecules in the presence of quenching ones. The software named PERRIN was written for FreeBASIC compiler and it can be applied for systems where the molecules remain static during its excited state lifetime. The good agreement found between the simulations and the expected theoretical results shows that it can be used for the luminescence and excited states decay kinetic teaching.

Determinação da constante de velocidade absoluta para a reação de abstração de hidrogênio fenólico pelo estado excitado triplete de xantona em acetonitrila e no líquido iônico hexafluorfosfato de 1-butil-3-metil-imidazólio [bmim.PF6]

The triplet excited state of xanthone was generated and characterized by laser flash photolysis in acetonitrile (λmax=620 nm; t=1.8 ms) and in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate [bmim.PF6] (λmax=620 nm; t=3.0 ms). It reacts with phenols yielding the corresponding xanthone ketyl radical. Stern-Volmer plots for the reaction of triplet xanthone with phenols led to the determination of absolute rate constants for phenolic hydrogen abstraction in the order of ~10(9) Lmol-1s-1 in acetonitrile and ~10(8) Lmol-1s-1 in [bmim.PF6]. The lower diffusioncontrolled rate constant for [bmim.PF6] is responsible for the difference in the phenolic hydrogen abstraction rate constants in this solvent.