Search results for "absorption spectroscopy"
showing 10 items of 828 documents
Generation of defects in amorphous SiO(2) assisted by two-step absorption on impurity sites.
2011
Generation of the Si dangling bond defect in amorphous SiO(2) (E' centre) induced by tunable pulsed UV laser radiation was investigated by in situ optical absorption measurements. The defect generation efficiency peaks when the photon energy equals ∼5.1 eV, it depends quadratically on laser intensity and is correlated with the native linear absorption due to Ge impurities. We propose a model in which the generation of E' is assisted by a two-step absorption process occurring on Ge impurity sites.
In situ measurements of molecular iodine in the marine boundary layer: the link to macroalgae and the implications for O<sub>3</…
2010
Abstract. Discrete in situ atmospheric measurements of molecular iodine (I2) were carried out at Mace Head and Mweenish Bay on the west coast of Ireland using diffusion denuders in combination with a gas chromatography-mass spectrometry (GC-MS) method. I2, IO and OIO were also measured by long-path differential optical absorption spectroscopy (LP-DOAS). The simultaneous denuder and LP-DOAS I2 measurements were well correlated (R2=0.80) but the denuder method recorded much higher concentrations. This can be attributed to the fact that the in situ measurements were made near to macroalgal sources of I2 in the intertidal zone, whereas the LP-DOAS technique provides distance-averaged mixing rat…
A new cell for the study of in situ chemical reactions using X-ray absorption spectroscopy
2005
An in situ cell for reductive and oxidative treatments at different temperatures that allows the possibility of recording data as a function of temperature has been designed and constructed for X-ray absorption experiments at the GILDA beamline BM08 of ESRF. The cell is linked to a mass quadrupole spectrometer providing control of the reaction gases and monitoring of the products. The apparatus allows measurements to be performed both in transmission and fluorescence geometry. The cell was tested by studying the CO oxidation reaction promoted by a Pt/ceria-zirconia-supported catalyst. The CO(2) yield is correlated with the structural results confirming the existence of a strong metal-suppor…
A theoretical study of the emission spectra of indole and its analogs: indene, benzimidazole, and 7-azaindole
2000
Abstract The complete active space (CAS) SCF method and multiconfigurational second-order perturbation theory (CASPT2) have been used to study the electronic spectra of indole, indene, benzimidazole, and 7-azaindole. The paper is focused on the study of the low-lying valence triplet and singlet electronic states at the optimized geometries of the excited states. The geometries have been optimized by using analytic CASSCF derivatives. CASPT2 point calculations have been performed in order to obtain band origins and relaxed emission energies. The results are analyzed in the context of the complex emission processes, both fluorescence and phosphorescence, displayed by the title compounds, whic…
A two-component model for the 2260cm−1 infrared absorption band in electron irradiated amorphous SiO2
2011
Abstract We report an experimental study by infrared absorption (IR) measurements focused on the effects of electron irradiation in the dose range from 1.2 × 10 3 kGy to 5 × 10 6 kGy on the intrinsic band peaked at 2260 cm − 1 in amorphous silicon dioxide (a-SiO 2 ) materials. This IR band is particularly relevant as it is assigned to an overtone of the strong asymmetric stretching vibration of Si–O–Si bridges and consequently it is intimately related to the Si–O–Si bond angle distribution. In a recent work we have shown that structural modifications induced by irradiation take place through the nucleation of confined high-defective and densified regions statistically dispersed into the w…
I.R. Experimental studies of dynamical aspects of water structure: Effects of HD substitution and of small solutes
1980
Abstract Results on i.r. absorption spectra of H2O, D2O and electrolytic solutions and their thermal modifications are presented. From the data, some parameters can be obtained which are suitable for a description of dynamical aspects of water structure. Solute induced changes of these parameters provide a quantitative, although phenomenologic description of the water-solute interaction.
Five-Coordinate Complexes [FeX(depe)2]BPh4, X = Cl, Br: Electronic Structure and Spin-Forbidden Reaction with N2
2002
The bonding of N(2) to the five-coordinate complexes [FeX(depe)(2)](+), X = Cl (1a) and Br (1b), has been investigated with the help of X-ray crystallography, spectroscopy, and quantum-chemical calculations. Complexes 1a and 1b are found to have an XP(4) coordination that is intermediate between square-pyramidal and trigonal-bipyramidal. Mössbauer and optical absorption spectroscopy coupled with angular overlap model (AOM) calculations reveal that 1a and 1b have (3)B(1) ground states deriving from a (xz)(1)(z(2))(1) configuration. The zero-field splitting for this state is found to be 30-35 cm(-1). In contrast, the analogous dinitrogen complexes [FeX(N(2))(depe)(2)](+), X = Cl (2a) and Br (…
Synthesis and characterisation of [(C5Me4R)2NbS2]2M complexes (M = Fe, Co; R = Me, Et) : organometallic tetrathiometalates with niobocene ligands
1996
Abstract Irradiation of Cp 2 ∗ Nb(η 2 S 2 )H (Cp ∗ = C 5 Me 5 ) 1a in the presence of Fe(CO) 5 gives the CO-free complex [Cp 2 ∗ NbS 2 ] 2 Fe 2a . The core of 2a contains an FeS 4 tetrahedron which is ligated by two niobocene ligands as shown by X-ray diffraction analysis. In the reaction of 1a or Cp 2 x Nb(η 2 S 2 )H (CP x = C 5 Me 4 Et) 1b with Co 2 (CO) 8 , compounds 3a and 3b of the same type are formed. Electrochemical studies of 2a and 3a,b show that they undergo three reversible 1e − steps. The oxidation of 3b exerts a considerable influence on its absorption spectrum. A qualitative EHMO analysis is in agreement with a strong delocalisation of electron density over the whole NbS 2 …
X‐ray Absorption Spectra of Cu II and Cu III Complexes of N , N ′ ‐1,2‐Phenylenebis(2‐mercapto‐2‐methylpropionamide)
2005
The X-ray absorption spectra of Cu I I and Cult complexes of N,N'-1,2-phenylenebis(2-mercapto-2-methylpropionamide) were recorded and analysed in solid phase. The EXAFS spectra of the two samples were refined with full multiple scattering path. Geometry optimisations on the Cu I I and Cu I I I complexes were performed by the B3LYP density functional method, with the 6-31G(d,p) basis set, considering different spin multiplicities. The singlet state of the Cu I I I complex was shown to be more stable than the triplet state, and a good agreement between the calculated and the corresponding experimental structure was found. Further single-point calculations on the optimised geometry were carrie…
Anchor‐Functionalized Push‐Pull‐Substituted Bis(tridentate) Ruthenium(II) Polypyridine Chromophores: Photostability and Evaluation as Photosensitizers
2014
Stable push-pull substituted heteroleptic bis(tridentate) ruthenium(II) polypyridine complexes with COOH or 2,2′-bipyridine anchor groups have been prepared and characterized by 1H, 13C and 15N NMR 1D and 2D spectroscopy, infrared spectroscopy, elemental analysis, high-resolution ESI mass spectrometry, electrochemistry, UV/Vis absorption spectroscopy, luminescence spectroscopy, and density functional calculations. The complexes feature a pronounced electronic directionality and high absorption wavelengths up to λmax = 544 nm extending to 720 nm as a result of favorable push-pull substitutions. A remarkable photostability in the presence of water and coordinating ions (I–) was discovered for…