A CASSCF/MRCI Study of the Low-Lying Electronic States of the BeS Molecule

Accurate potential energy curves, dipole moment functions, dissociation energies, and molecular constants for several low-lying singlet and triplet electronic states of BeS were investigated using the CASSCF/MRCI methodology, and the cc-pV5Z basis set for beryllium, and the aug-cc-pV(5+d) Z set for sulfur. Besides presenting improved results for the three lowest lying states, this study presents the first theoretical characterization of another set of nine excited states so far unknown experimentally. Our results are sufficiently accurate to reliably guide the experimental search and characterization of these states, and also to confirm the experimental assignment of the B(1)Sigma(+) excited state. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1694-1700, 2011

Fluorescent probes with malononitrile side group in methyl methacrylate copolymers

Fluorescent probes derivated from auramine, 1-aminopyrene, and 9-aminoacridine containing a malononitrile group are copolymerized with methyl methacrylate. These new fluorescent polymeric materials are studied in solution of different solvents by steady-state and time-resolved emission techniques. Their spectroscopic properties and excited state dynamics are driven by charge transfer from the aromatic group to the electron withdrawing CN groups, and this factor is responsible for the non-exponential emission decay behavior. (c) 2008 Elsevier B.V. All rights reserved.

Photodegradation of Folate Sensitized by Riboflavin

Folate is shown to react with singlet-excited state of riboflavin in a diffusion controlled reaction and with triplet-excited state of riboflavin in a somewhat slower reaction with (3)k(q) = 4.8 x 10(8) L mol(-1) s(-1) in aqueous phosphate buffer at pH 7.4, ionic strength of 0.2 mol L(-1), and 25 degrees C. Singlet quenching is assigned as photo-induced reductive electron transfer from ground state folate to singlet-excited riboflavin, while triplet quenching is assigned as one-electron transfer rather than hydrogen atom transfer from folate to triplet-excited riboflavin, as the reaction quantum yield, phi = 0.32, is hardly influenced by solvent change from water to deuterium oxide, phi = 0.37. Cyclic voltammetry showed an irreversible two-electron anodic process for folate, E = 1.14 V versus NHE at a scan-rate of 50 mV s(-1), which appears to be kinetically controlled by the heterogeneous electron transfer from the substrates to the electrode. Main products of folate photooxidation sensitized by riboflavin were pterin-6-carboxylic acid and p-aminobenzoyl-L-glutamic acid as shown by liquid chromatographic ion-trap mass spectrometry (LC-IT-MS).

Laurdan Spectrum Decomposition as a Tool for the Analysis of Surface Bilayer Structure and Polarity: a Study with DMPG, Peptides and Cholesterol

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Three helium atoms and the scaling limit

We show that a scaling limit approach, previously applied in three-body low-energy nuclear physics, is realized for the first excited state of He-4 trimer. The present result suggests that such approach has a wider application.

Charged three-body system with arbitrary masses near conformal invariance

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Time dependence and energy-transfer mechanisms in Tm3+Ho3+ and Tm3+-Ho3+ co-doped alkali niobium tellurite glasses sensitized by Yb3+

Glass samples with the composition (mol%) 80TeO(2)-10Nb(2)O(5)-5K(2)O-5Li(2)O, stable against crystallization, were prepared containing Yb3+, Tm3+ and Ho3+. The energy transfer and energy back transfer mechanisms in samples containing 5% Yb3+-5% Tm3+ and 5% Yb3+-5% Tm3+-0.5% Ho3+ were estimated by measuring the absorption and fluorescence spectra together with the time dependence of the Yb3+ F-2(5/2) excited state. A good fit for the luminescence time evolution was obtained with the Yokota-Tanimoto's diffusion-limited model. The up-conversion fluorescence was also studied in 5% Yb-5% Tm. 5% Yb-0.5% Ho and 5% Yb-5% Tm-0.5% Ho tellurite glasses under laser excitation at 975 nm. Strong emission was observed from (1)G(4) and F-3(2) Tm3+ energy levels in all samples. The S-5(2) Ho3+ emission was observed only in Yb3+Ho3+ samples being completely quenched in Yb3+/Tm3+/Tm3+ samples. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Optical spectroscopy and frequency upconversion properties of Tm3+ doped tungstate fluorophosphate glasses

Tungstate fluorophosphate glasses of good optical quality were synthesized by fusion of the components and casting under air atmosphere. The absorption spectra from near-infrared to visible were obtained and the Judd-Ofelt parameters determined from the absorption bands. Transition probabilities, excited state lifetimes and transition branching ratios, were, determined from the measurements. Pumping with a 354.7 nm beam from a pulsed laser. resulted in emission at 450 nm. due to transition D-1(2)-->F-3(4) in Tm3+ ions and a broadband emission centered at approximate to 550 nm attributed to the glass matrix. When pumping at 650 nm, two emission bands at 450 nm (D-1(2)-->F-3(4)) and at 790 nm (H-3(4)-->H-3(6)) were observed. Excitation spectra were also obtained in order to understand the origin of both emissions. Theoretical and experimental lifetimes were determined and,the results were explained in terms of multiphonon relaxation. (C) 2003 American Institute of Physics.

Red, green, and blue upconversion luminescence in ytterbium-sensitized praseodymium-doped lead-cadmium-germanate glass

Blue, green, red, and near-infrared upconversion luminescence in the wavelength region of 480-740 nm in Pr3+/Yb3+-codoped lead-cadmium-germanate glass under 980 nm diode laser excitation, is presented. Upconversion emission peaks around 485, 530, 610, 645, and 725 nm which were ascribed to the P-3(0)-H-3(J) (J = 4, 5, and 6), and P-3(0)-F-3(J) (J = 2, 3, and 4), transitions, respectively, were observed. The population of the praseodymium upper P-3(0) emitting level was accomplished through a combination of ground-state absorption of Yb3+ ions at the F-2(7/2), energy-transfer Yb3+(2F(5/2))-Pr3+(H-3(4)), and excited-state absorption of Pr3+ ions provoking the (1)G(4)-P-3(0) transition. The dependence of the upconversion luminescence upon the Yb3+-concentration and diode laser power, is also examined, in order to subsidize the proposed upconversion excitation mechanism. (C) 2004 Elsevier B,V. All rights reserved.

EXAFS, SAXS and Eu3+ luminescence spectroscopy of sol-gel derived siloxane-polyethyleneoxide hybrids

Hybrid Eu3+-doped silica-poliethyleneoxide (PEO) nanocomposites with covalent bonds between the inorganic (siloxane) and organic (PEO) phases have been obtained by sol-gel process. These materials are transparent, flexible and present high Eu3+ luminescence output. Their luminescence properties, local environment around europium ions and structure have been investigated as a function of europium content. EXAFS measurements indicate that the increase in Eu-doping induces a decrease in Eu3+ coordination number. An increase in symmetry degree around the metal ion is also observed for increasing Eu3+ concentration, while non radiative decay paths from the D-5(0) excited state become more important. SAXS results suggest the preferential interaction of europium ions with ether-type oxygens of the polymer chains. However, the existence of interactions between the cations and the carbonyl groups from urea bridges located at the siloxane-PEO interface can not be excluded.

Infrared and far-infrared spectroscopy of (CH3OH)-C-13: TeraHertz laser lines and assignments

We use a (CO2)-C-13 laser as optical pumping source to search for new THz laser lines generated from (CH3OH)-C-13. Nineteen new THz laser lines (also identified as far-infrared, FIR) ranging from 42.3 mu m (7.1 THz) to 717.7 mu m (0.42 THz) are reported. They are characterized in wavelength, offset, relative polarization, relative intensity, and optimum working pressure. We have assigned eight laser lines to specific rotational energy levels in the excited state associated with the C-O stretching mode. (c) 2006 Elsevier B.V. All rights reserved.

O comportamento fotoquímico dos complexos pentaaminas de rutênio(II) com ligantes pi insaturados

A general overview on the photochemical behaviour of [Ru(NH3)(5)L](2+) complexes (where L is a pi 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)(5)py](2+) complex.

Analysis of the ethidium bromide bound to DNA by photoacoustic and FTIR spectroscopy

Under physiological conditions B-form DNA is an exceedingly stable structure. However, experimental evidences obtained through nuclear magnetic resonance and fluorescence anisotropy suggest that the structure of the double helix fluctuates substantially. We describe photoacoustic phase modulation frequency measurements of ethidium bromide (Eb) with calf thymus, DNA. As in fluorescence phase modulation measurements, we used an intercalating dye as a probe; however, we monitored the triplet excited state lifetime at different ionic strengths. The triplet lifetime of Eb varied from about 0.30 ms, with no DNA present, to 20 ms, (at a DNA:Eb molar ratio of 5). With salt titration, this value falls, to about 2.0 ms. This result suggests, a strong coupling between the phenantridinium ring of the ethidium and the base pairs because of the stacking movement of the DNA molecule under salt effect. This, effect may be understood considering DNA as a polyelectrolyte. The counterions, in the solution shield the phosphate groups, reducing the electrostatic repulsion force between them, hence compacting the DNA molecule. The results from Fourier transform infrared demonstrated two important bands: 3187 cm(-1) corresponding to the symmetric stretching of the NH group of the bases, and 1225 cm(-1) corresponding to the asymmetric stretching of phosphate groups shifted toward higher wavenumbers, suggesting a proximity between the intercalant and base pairs and a modification of the DNA backbone state, both induced by salt accretion.

Spectroscopic properties of polycarbonate and poly(methyl methacrylate) blends doped with Europium(III) acetylacetonate

Spectroscopic properties of blends formed by bisphenol-A polycarbonate (PC) and poly(methyl methacrylate) (PMMA) doped with Europium (III) acetylacetonate [Eu(acac)(3)], have been studied by photoacoustic spectroscopy (PAS) and photoluminescent (PL) spectroscopy. Emission and excitation spectra, excited state decay times, and quantum efficiency have been evaluated as well. PAS studies evidenced chemical interactions between the Europium complex and the PC/PMMA blend, which presented typical percolation threshold behavior regarding the Eu3+ content. PL spectra evidenced the photoluminescence of the Eu3+ incorporated into the blend. Photoluminescence property enhancement was observed for the composite in comparison with the precursor compound. Optimized emission quantum efficiency was observed for the 60/40 blend doped with 2% and 4% Europium (III) acetylacetonate. (c) 2005 Elsevier B.V. All rights reserved.

MAGNETOOPTICAL PROPERTIES OF F-2(+) CENTER IN KCL-SH-

The magnetic circular dichroism (MCD) of F2+ centers in KCl:SH- has been measured in absorption in the 1ssigma(g) --> 2p(y)pi(u) transitions at 493 and 509 nm, with fields up to 5 T and in the temperature range 1.5 K < T < 77 K. Within the limit of detection, no MCD is observed in the near infrared transition 1ssigma(g) --> 2psigma(u) as well as in both emissions 2ppi(u) --> 1ssigma(g) and 2psigma(u) --> 1ssigma(g). The optical detection of EPR in the F2+ ground state presents an isotropic single band with g = 1.965 +/- 0.007. The spin-lattice relaxation measured at H = 0.32 T is typical of a direct process T-1 = 4.3 x 10(-2_ coth (gmu(B)H/2k(B)T). The spectral variation of the MCD is calculated using perturbation theory to first order. The Hamiltonian includes the spin-orbit interaction in the 2ppi(u) excited state and the orbital molecular wave functions are obtained by a linear combination of 1s and 2p atomic orbitals. The calculated MCD is in good agreement with the observed one, for the spin-orbit interaction strength Pound(z) = 3.6 meV.