Photodesorption of O<Subscript>2</Subscript> from Ag<Subscript>2</Subscript><Superscript>-</Superscript>: A time-resolved study of Ag<Subscript>2</Subscript>O<Subscript>2</Subscript><Superscript>-</Superscript>

We present time-resolved photoelectron spectra of mass-selected Ag₂O₂ anions. The anions are photoexcited by photons with an energy of 3.1 eV, and photoelectron spectra of the excited species Ag₂O₂ ^{- *} and the subsequently appearing fragments are recorded using a probe laser pulse with a photon energy of 1.5 eV. The excited state of Ag₂O₂ ^- has a short lifetime of 130 fs±70 fs only and decays by direct photodesorption of O₂. The data demonstrate the ability of time-resolved photoelectron spectroscopy (TR-PES) to observe the breaking of chemical bonds if the decay process of the excited state is direct (non-thermal desorption). The data are compared to recent results of a NeNePo experiment [1] on the same system. PACS 68.43.Tj; 78.47.+p; 33.80.Eh; 36.40.-c     

Nonradiative relaxation of photoexcited O<Stack><Subscript>1</Subscript><Superscript>0</Superscript></Stack> centers in glassy SiO<Subscript>2</Subscript>

The processes involved in the excited-state relaxation of hole O ₁ ⁰ centers at nonbridging oxygen atoms in glassy SiO₂ were studied using luminescence, optical absorption, and photoelectron emission spectroscopy. An additional nonradiative relaxation channel, in addition to the intracenter quenching of the 1.9-eV luminescence band, was established to become operative at temperatures above 370 K. This effect manifests itself in experiments as a negative deviation of the temperature-dependent luminescence intensity from the well-known Mott law and is identified as thermally activated external quenching with an energy barrier of 0.46 eV. Nonradiative transitions initiate, within the external quenching temperature interval, the migration of excitation energy, followed by the creation of free electrons. In the final stages, this relaxation process becomes manifest in the form of spectral sensitization of electron photoemission, which is excited in the hole O ₁ ⁰ -center absorption band.     

H<Subscript>3</Subscript>O<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack> ions with a strong quasi-symmetrical H-bond and their hydration in aqueous solutions of NaOH and KOH

Ion-molecular interactions in aqueous solutions of NaOH (0–47.8%) and KOH (0–51.95%) are studied by multiple frustrated total internal reflection IR spectroscopy. Interpretation of the spectra and analysis of the spectral data are performed based on the results of DFT calculations (B3LYP/6-31++G(d, p)) of the characteristics of the free and double hydrated H₃O ₂ ^- ion. It is established that the changes in the IR spectra of NaOH and KOH aqueous solutions caused by increasing alkali concentration are due to the formation of H₃O ₂ ^- ions with a strong quasi-symmetrical hydrogen bond and their subsequent hydration by one or two water molecules. The influence of the cation nature on the degree of hydration of H₃O ₂ ^- ions is demonstrated. The equilibrium concentrations of monohydrate (H₃O ₂ ^- ? H₂O) and dihydrate (H₃O ₂ ^- ? 2H₂O) are calculated and their IR continuous absorption spectra are isolated.     

Experimental evidence for molecular ultrafast dissociation in O<Subscript>2</Subscript> clusters

Resonant Auger spectra of O₂ clusters excited at the O1s edge are reported. After excitation to the repulsive 1s^-13σ^* state, the resulting resonant Auger spectrum displays features that remain constant in kinetic energy as the photon energy is detuned. The shift between known atomic fragment features and these features is consistent with that observed for atoms and clusters in singly charged states in direct photoemission. These findings are strong evidence for the existence of molecular ultrafast dissociation processes within the clusters or on their surface.     

Metastable helium cluster He<Stack><Subscript>4</Subscript><Superscript>*</Superscript></Stack>

The existence of a metastable cluster He ₄ ^* with total spin S = 2 is predicted. The cluster consists of two covalently bound excited spin-polarized triplet He ₂ ^* molecules and is rectangular in shape. The electron wavefunctions, the dependence of the energy He ₄ ^* system on the distance between the He ₂ ^* triplet molecules, the atomic spacing, the frequency spectrum of natural oscillations of the cluster, and other characteristics are calculated from first principles. It is shown that the metastable state is formed if one of the excited He ₂ ^* molecules is in the ³Σ _u ⁺ state, while the other is in the ³Π_g state. The radiation lifetime τ of the metastable cluster He ₄ ^* is calculated; it is found to range from 100 to 200 s, which is much longer than the lifetime τ ≈ 20 s of the triplet molecule He ₂ ^* (³Σ _u ⁺ ). The height U ≈ 0.5 eV of the potential barrier preventing the departure from the local energy minimum is determined. The energy E_acc ≈ 9 eV/atom accumulated in the He ₄ ^* cluster is calculated; this energy considerably exceeds the energy of known chemical energy carriers. It is shown that the accumulated energy is released virtually completely during decomposition of the He ₄ ^* cluster into individual helium atoms. This means that helium clusters are a promising material with a high accumulated energy density (HEDM).     

Crystal field analysis of the ground and excited state absorption of a Cr<Superscript>4+</Superscript> ion in LiAlO<Subscript>2</Subscript> and LiGaO<Subscript>2</Subscript> crystals

The exchange charge model of crystal field theory has been used to analyze the ground and excited state absorption of tetrahedrally coordinated Cr⁴⁺ ion in lithium aluminum oxide LiAlO₂ (γ-phase) and lithium dioxogallate LiGaO₂. The parameters of the crystal field acting on the Cr⁴⁺ ion are calculated from the crystal structure data, taking into account the crystal lattice ions located at distances up to 12.744 Å in LiGaO₂ and 13. 180 Å in LiAlO₂. The obtained energy level schemes were compared with experimental ground and excited state absorption spectra and literature data on the application of other crystal field models (the angular overlap model and Racah theory) to the considered crystals; a good agreement with experimental data is demonstrated.     

Spectroscopic Properties and Energy Transfer Analysis of Tm<Superscript>3+</Superscript>-Doped BaF<Subscript>2</Subscript>-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript> Glass

This paper reports on the spectroscopic properties and energy transfer analysis of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂-La₂O₃ glasses with different Tm₂O₃ doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm−2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm³⁺, cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm₂O₃ doping concentrations. The maximum fluorescence intensity at around 1.8 μm has been obtained in Tm₂O₃-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm³⁺ in this sample is about 0.48 × 10⁻²⁰ cm² at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm³⁺-doped BaF₂-Ga₂O₃-GeO₂- La₂O₃ glass for 2.0-μm optical fiber laser.     

Kinetics of Rb<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> and Rb<Superscript>+</Superscript> formation in laser-excited rubidium vapor

We have studied the formation of the molecular ion Rb₂⁺ and the atomic ion Rb⁺. These are created in laser excited rubidium vapor at the first resonance, 5s–5p and 5p-nl transitions. A theoretical model is applied to this interaction to explain the time evolution and the laser-power dependence of the population density of Rb⁺ and Rb₂⁺. A set of rate equations which describe: the temporal variation of the population density of the excited states; the atomic ion density; and the electron density, were solved numerically under the experimental conditions of Barbier and Cheret. In their experiment the Rb concentration was 1×10¹³cm⁻³ and the laser power was taken to be 50–500 mW at vapor temperature = 450 K. The results showed that the main processes for producing Rb₂⁺ are associative ionization and Hornbeck-Molnar ionization. The calculations have also showed that, the atomic ions Rb⁺ are formed through the Penning Ionization (PI) and photoionization processes. Moreover, a reasonable agreement between the experimental results and our calculations for the ion currents of the Rb⁺ and Rb₂⁺ is obtained.      

Luminescence thermometry using Gd<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>3+</Superscript>

In this paper we study the possibility of using the synthesized nanopowder samples of Gd₂Zr₂O₇:Eu³⁺ for temperature measurements by analyzing the temperature effects on its photoluminescence. The nanopowder was prepared by solution combustion synthesis method. The photoluminescence spectra used for analysis of Gd₂Zr₂O₇:Eu³⁺ nano phosphor optical emission temperature dependence were acquired using continuous laser diode excitation at 405 nm. The temperature dependencies of line emission intensities of transitions from ⁵D₀ and ⁵D₁ energy levels to the ground state were analyzed. Based on this analysis we use the two lines intensity ratio method for temperature sensing. Our results show that the synthesized material can be efficiently used as thermographic phosphor up to 650 K.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

Research of the Spin-Hamiltonian Parameters and Defect Structure for the Trigonal Mn<Superscript>4+</Superscript> Centers in Y<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>:Mn<Superscript>4+</Superscript> Crystal

The high-order perturbation formulas founded on the two-mechanism model are applied in this paper to compute the spin-Hamiltonian parameters (g factors g _//, g _⊥ and zero-field splitting D) of the trigonal Mn⁴⁺ centers in Y₂Ti₂O₇:Mn⁴⁺ crystal. In this model, besides the contributions from the traditional crystal-field (CF) mechanism (in the CF theory) related to CF excited states, those from the charge-transfer (CT) mechanism connected with CT excited states are contained. The calculated results are reasonably coincident with the observed values. The calculations show that the contributions of CT mechanism to spin-Hamiltonian parameters (in particular, the g factors) for (MnO₆)^8? clusters are large and cannot be neglected. The defect structure of trigonal (MnO₆)^8? clusters in Y₂Ti₂O₇:Mn⁴⁺ crystals is also evaluated. The results are discussed.     

Polymerization of solid C<Subscript>60</Subscript> under C<Stack><Subscript>60</Subscript><Superscript>+</Superscript></Stack> cluster ion bombardment

The structure transformation occurring in fullerene film under bombardment by 50 keV C₆₀⁺ cluster ions is reported. The Raman spectra of the irradiated C₆₀ films reveal a new peak rising at 1458 cm⁻¹ with an increase in the ion fluence. This feature of the Raman spectra suggests linear polymerization of solid C₆₀ induced by the cluster ion impacts. The aligned C₆₀ polymeric chains composing about 5–10 fullerene molecules have been distinguished on the film surface after the high-fluence irradiation using atomic force microscopy (AFM). The surface profiling analysis of the irradiated films has revealed pronounced sputtering during the treatment. The obtained results indicate that the C₆₀ polymerization occurs in a deep layer situated more than 40 nm below the film surface. The deep location of the C₆₀ polymeric phase indirectly confirms the dominant role of shock waves in the detected C₆₀ phase transformation.     

A miniature tunable TEA CO<Subscript>2</Subscript> laser using isotope <Superscript>13</Superscript>C<Superscript>16</Superscript>O<Subscript>2</Subscript> and <Superscript>12</Superscript>C<Superscript>16</Superscript>O<Subscript>2</Subscript>

A miniature tunable TEA CO₂ laser using isotope ¹³C¹⁶O₂ as the active medium is developed to extend the spectral range of CO₂ lasers for further application. The optimization of the energy parameters of the tunable TEA ¹³C¹⁶O₂ laser and the same laser using ¹²C¹⁶O₂ are studied. When a gas mixture (¹³C¹⁶O₂: N₂: He = 1: 1: 3) at a total pressure of 6.4 × 10⁴ Pa is used, the TEA ¹³C¹⁶O₂ laser of a 45-cm³ active volume obtains 51 emission lines in the [00⁰1–10⁰0] and [00⁰1–02⁰0] bands. The maximum pulse energy of the TEA ¹³C¹⁶O₂ laser is about 357 mJ. The same laser using the conventional gas mixture (¹²C¹⁶O₂: N₂: He = 1: 1: 3) at a pressure of 6.66 × 10⁴ Pa is measured to obtain 69 laser emission lines and the maximum pulse energy of laser radiation is about 409 mJ.     

Recognition of H<Subscript>2</Subscript>PO<Stack><Subscript>4</Subscript><Superscript>-</Superscript></Stack> and Cu<Superscript>2+</Superscript> in Water by Luminescent Terbium Silica Xerogel

Terbium silica hybrid material with imidazole ring that can be emissive in water has been designed and showed host-guest interactions with specific ions (cations and anions). In detail, we studied the sensing abilities of this material by addition of the anions H₂PO₄^-, HSO₄^-, F^-, Cl^-, Br^- and I^- to water suspension of the derived powders. Only dihydrogen phosphate resulted in the quenching of the lanthanide luminescence (detection limit 10^-5 M). The same way was found in Cu²⁺ ions which also gave rise to luminescence quenching (detection limit 10^-5 M). More interestingly, luminescent sol-gel films were successfully prepared by the same materials and exhibited emission responses to H₂PO₄^- and Cu²⁺. For the sake of improving its mechanical property, the robust and flexible inorganic/PMMA hybrid material with sensing capability was also developed for future use.     

Synthesis and Optical Characterization of Red-Emitting BaTa<Subscript>2</Subscript>O<Subscript>6</Subscript>:Eu<Superscript>3+</Superscript> Phosphors

Undoped and Eu³⁺ doped BaTa₂O₆ phosphors were synthesized via solid state reaction method and characterized by using XRD, SEM-EDS and photoluminescence (PL) analyses. The XRD results revealed that the crystal structure of BaTa₂O₆ allowed up to 10 mol% levels of Eu³⁺ ions due to the TTB characteristic network of adjacent octahedrals. SEM-EDS analyses confirmed the formation of BaTa₂O₆ structure and EuTaO₄ secondary phase. BaTa₂O_6:Eu³⁺ phosphors exhibited orange and red emissions at 592.2 nm and 615.7 nm in the visible region respectively. The Commission Internationale d’Eclairage (CIE) chromaticity coordinates of the BaTa₂O_6:Eu³⁺ phosphors that excited at λ _ex = 400 nm ranged from orangish-red to pinkish-red depending on increasing Eu³⁺ concentration.     

Dissociation channels of silver bromide cluster Ag<Subscript>2</Subscript>Br,silver cluster Ag<Subscript>3</Subscript> and their ions studied by using alkali metal target

Various dissociation channels of silver bromide cluster ion Ag₂Br⁺ and silver cluster ion Ag₃ ⁺ were observed in high-energy collisionally-activated dissociation (CAD) using a Cs target. The fragment patterns of the high-energy CAD were compared with those of the metastable dissociation and low-energy CAD. The difference in the fragment patterns between the high-energy CAD and the other dissociation methods was explained in terms of the internal energy distributions. The dissociation mechanisms of neutral silver bromide cluster Ag₂Br and silver cluster Ag₃ were also investigated by charge inversion mass spectrometry using the Cs target. While the fragment ions AgBr^- and Ag₂ ^- were dominantly observed in the charge inversion spectrum of Ag₂Br⁺, the undissociated ion Ag₃ ^- was observed as a predominant peak in the case of Ag₃ ⁺. The dissociation behavior of Ag₂Br^* can be explained on the basis of the calculated thermochemical data. Contrary to this, the predominant existence of the undissociated Ag₃ ^- cannot be explained by the reported thermochemical data. The existence of undissociated Ag₃ ^- suggests that the dissociation barrier is higher than the internal energy of Ag₃ ^* (theoretical: 1.03 eV, experimental: 2.31 eV) estimated from the ionization potentials of Ag₃ and Cs.     

Spectroscopy and energy balance of the Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> selective emission upon the laser thermal excitation

The laser thermal melting of powders is used to fabricate selective emitters (SEs) that represent Nd₂O₃ and Y₂O₃-Nd₂O₃ polycrystals on quartz holders. The SEs are stable under atmospheric conditions upon multiple heating by laser radiation up to the melting point. The spectral shape and integral intensity of the selective heat radiation (SHR) of the Nd₂O₃ microcrystalline powder and the Nd₂O₃ and Y₂O₃-Nd₂O₃ polycrystals are experimentally studied in the near-IR and visible spectral ranges versus the intensity of the laser thermal excitation at a wavelength of 10.6 μm in comparison with the absorption and luminescence spectra of the YAG:Nd³⁺ and YAlO₃:Nd³⁺ single crystals. The SHR spectra are determined by the vibronic transitions between the electronic states ² G _7/2-⁴F_3/2 ⁴I_11/2 and ⁴I_9/2 of the Nd³⁺ ions that are thermally excited due to the multiphonon transitions from the ground state. The energy balance of the SE laser thermal heating is experimentally investigated. The coefficient of the laser energy conversion to the Nd³⁺ SHR is measured, and the emissivity of the SEs that can be used for the study of the thermophotovoltaic generators and the optical excitation of the laser-active media in the near-IR spectral range is estimated.     

Photophysics of C<Subscript>60</Subscript> and C<Subscript><Emphasis Type="Bold">60</Emphasis></Subscript><Superscript><Emphasis Type="Bold">-</Emphasis></Superscript> in faujasite zeolites

While the intercalation of C₆₀ and the formation of C ₆₀ ^- in the supercages of NaX and NaY are confirmed by using ¹²⁹Xe NMR and ESR, the photophysical properties of C₆₀ and C ₆₀ ^- are characterized by monitoring transient reflectance spectra and kinetics, fluorescence kinetics, and diffuse reflectance spectra. C ₆₀ ^- is considerably more abundant in NaY than in NaX. This difference is explained in terms of polarity difference between two zeolites. Both C₆₀ and C ₆₀ ^- have remarkably elongated excited-state lifetimes due to their collision-free environment in zeolitic nanocavities although C ₆₀ ^- has much shorter lifetimes than C₆₀. C ₆₀ ^- , in particular, shows intense absorption and emission due to its reduced symmetry in zeolites. Received 13 July 2001 and Received in final form 8 October 2001     

Pulsed laser deposition of BaGa<Subscript>2</Subscript>O<Subscript>4</Subscript>

This paper reports the first results obtained on monobarium gallate thin films grown on silicon and platinum coated substrates by pulsed laser deposition. The influence of oxygen background pressure and substrate (or post-annealing) temperature on the film properties was studied. The films were characterized by XRD, RHEED, AFM, photoelectron and electrical impedance spectroscopy. The structure analysis showed that the films crystallized into a hexagonal phase, most probably into (metastable) α-BaGa₂O₄. Depending on deposition conditions, films with different (from nearly epitaxial to polycrystalline) textures were obtained.     

Photolumiscent Properties of Nanorods and Nanoplates Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

Nanorods and nanoplates of Y₂O₃:Eu³⁺ powders were synthesized through the thermal decomposition of the Y(OH)₃ precursors using a microwave-hydrothermal method in a very short reaction time. These powders were analyzed by X-ray diffraction, field emission scanning electron microscopy, Fourrier transform Raman, as well as photoluminescence measurements. Based on these results, these materials presented nanoplates and nanorods morphologies. The broad emission band between 300 and 440 nm ascribed to the photoluminescence of Y₂O₃ matrix shifts as the procedure used in the microwave-hydrothermal assisted method changes in the Y₂O₃:Eu³⁺ samples. The presence of Eu³⁺ and the hydrothermal treatment time are responsible for the band shifts in Y₂O₃:Eu³⁺ powders, since in the pure Y₂O₃ matrix this behavior was not observed. Y₂O₃:Eu³⁺ powders also show the characteristic Eu³⁺ emission lines at 580, 591, 610, 651 and 695 nm, when excited at 393 nm. The most intense band at 610 nm is responsible for the Eu³⁺ red emission in these materials, and the Eu³⁺ lifetime for this transition presented a slight increase as the time used in the microwave-hydrothermal assisted method increases.