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101.
102.
Solà Vázquez A Martín A Costa-Fernandez JM Ruiz Encinar J Bordel N Pereiro R Sanz-Medel A 《Analytical and bioanalytical chemistry》2007,389(3):683-690
There is an increasing concern regarding the toxicity and environmental distribution and impact of brominated organic compounds
employed as flame retardants. Thus, present interest in searching for new analytical techniques and methods allowing a rapid,
simple and reliable detection of those compounds in materials and wastes potentially containing such flame retardants is not
surprising. The feasibility of using radiofrequency glow discharge plasma spectrometry coupled with optical emission spectrometry
(rf-GD-OES) as a rapid and simple tool to directly analyse bromine-containing flame-retardant polymeric layers is investigated
here. Polymeric layers for calibration were made by mixing appropriate amounts of tetrabromobisphenol A, bisphenol A, phloroglucinol
and diphenylmethane-4,4′-diisocyanate in tetrahydrofuran. The corresponding blanks (polymers without tetrabromobisphenol A)
were also prepared. Detection of bromine was investigated both in the visible (at 470.48 nm) and in the near-infrared (at
827.24 nm) regions, using a charge-coupled device for detection. Discharge parameters affecting the emission intensity of
bromine were first optimized (in argon and helium as possible plasma gases) and the analytical performance characteristics
were then evaluated. The best detection limit (0.044% Br) was achieved measuring Br I 827.24 nm in a He discharge, using a
forward power of 70 W and a pressure of 45 Torr. The linearity range extended up to 27% Br. Finally, the applicability of
the rf-GD-OES method proposed to the quantitative analysis of bromine in solid materials coated with flame-retardant commercial
paints was successfully demonstrated.
Figure Flame Retardants 相似文献
103.
Proper normalization of two previously published indices yields aromaticity measures that, when computed within the Hückel molecular orbital (HMO) approximation, closely match the topological resonance energies per pi electron of aromatic annulenes and their ions. The normalized indices, which quantify aromaticity of individual rings in polycyclic systems, are equally applicable to homocyclic and heterocyclic compounds and can be readily computed from 1-matrices calculated at any level of electronic structure theory. However, only the index ING, derived from the Giambiagi formula, produces proper ordering of aromaticities of heterocyclic compounds, provided it is calculated from all-electron wavefunctions in conjunction with the atoms in molecule (AIM) partitioning. Its values are shown to be strongly affected by electron correlation effects. Because of its apparent inability to distinguish between anti- and nonaromatic systems, ING should only be employed for aromatic species. 相似文献
104.
We have investigated table salt and other alkali metal chloride monomers, ClM, and (distorted) cubic tetramers, (ClM)(4), with M = Li, Na, K, and Rb, using density functional theory (DFT) at the BP86/TZ2P level. Our objectives are to determine how the structure and thermochemistry (e.g., Cl-M bond lengths and strengths, oligomerization energies, etc.) of alkali metal chlorides depend on the metal atom and to understand the emerging trends in terms of quantitative Kohn-Sham molecular orbital (KS-MO) theory. The analyses confirm the high polarity of the Cl-M bond (dipole moment, VDD, and Hirshfeld atomic charges). They also reveal that bond overlap derived stabilization (approximately -26, -20, and -8 kcal/mol), although clearly larger than in the corresponding F-M bonds, contributes relatively little to the (trend in) bond strengths (-105, -90, and -94 kcal/mol) along M = Li, Na, and K. Thus, the Cl-M bonding mechanism resembles more closely that of the even more ionic F-M bond than that of the more covalent C-M or H-M bonds. Tetramerization causes the Cl-M bond to expand, and it reduces its polarity. 相似文献
105.
Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals 总被引:2,自引:0,他引:2
M.C. Pujol M. Rico C. Zaldo R. Solé V. Nikolov X. Solans M. Aguiló F. Díaz 《Applied physics. B, Lasers and optics》1999,68(2):187-197
4 )2 single crystals doped with Er3+ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined,
being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) Å, β=130.80(2)°. The refractive index dispersion of the host
has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er3+ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet
splittings expected for the C2 symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated
as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the
4F7/2 multiplet. The Judd–Ofelt (JO) parameters of Er3+ in KGW have been calculated: Ω2=8.90×10-20 cm2, Ω4=0.96×10-20 cm2, Ω6=0.82×10-20 cm2. Lifetimes of the 4S3/2, 4F9/2, and 4I11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory.
A reduction of the 4S3/2 and 4I11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative
processes is inferred from the temperature dependence of the lifetimes.
Received: 15 December 1997/Revised version: 10 July 1998 相似文献
106.
Dr. Mauricio Rodríguez-Mayorga Dr. Eloy Ramos-Cordoba Prof. Xabier Lopez Prof. Miquel Solà Prof. Jesus M. Ugalde Dr. Eduard Matito 《ChemistryOpen》2019,8(4):411-417
We analyze the Coulomb hole of Ne from highly-accurate CISD wave functions obtained from optimized even-tempered basis sets. Using a two-fold extrapolation procedure we obtain highly accurate results that recover 97 % of the correlation energy. We confirm the existence of a shoulder in the short-range region of the Coulomb hole of the Ne atom, which is due to an internal reorganization of the K-shell caused by electron correlation of the core electrons. The feature is very sensitive to the quality of the basis set in the core region and it is not exclusive to Ne, being also present in most of second-row atoms, thus confirming that it is due to K-shell correlation effects. 相似文献
107.
Fran?ois B Vialatte Jordi Solé-Casals Justin Dauwels Monique Maurice Andrzej Cichocki 《BMC neuroscience》2009,10(1):46
Background
oscillatory activity, which can be separated in background and oscillatory burst pattern activities, is supposed to be representative of local synchronies of neural assemblies. Oscillatory burst events should consequently play a specific functional role, distinct from background EEG activity – especially for cognitive tasks (e.g. working memory tasks), binding mechanisms and perceptual dynamics (e.g. visual binding), or in clinical contexts (e.g. effects of brain disorders). However extracting oscillatory events in single trials, with a reliable and consistent method, is not a simple task. 相似文献108.
Víctor March Manuel Arrayás José Luis Trueba Joan Montanyà David Romero Glòria Solà Daniel Aranguren 《Journal of Electrostatics》2009,67(2-3):301-306
A numerical study of laser-triggered discharges in air at atmospheric pressure is presented for an ultraviolet laser in small gaps. Two models, one for the ionization of the air by the laser pulse and the second for the streamer evolution have been computed. From results of numerical simulations the influence of the laser parameters such as energy, pulse duration and beam radius is analyzed and electron distributions are obtained for different small gaps. Electric field, streamer velocity and evolution of the ionized volume are calculated by means of streamer simulations. This paper shows the main features of the laser-triggered discharges and also the importance of using numerical simulations in a laser-triggered experiment. 相似文献
109.
J. Oscar C. Jimenez‐Halla Miquel Solà Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(45):12503-12520
We have carried out a theoretical investigation of the Dötz reaction between acetylene and a series of chromium Fischer‐type carbenes [(CO)5Cr?C(X)R] with different representative substituents (R=CH?CH2, Ph) and heteroatom ligands (X=OH, NH2, OCH3, N(CH3)2) by using density functional theory with the B3LYP functional. We have studied the Dötz and chromahexatriene mechanisms of benzannulation and also the reaction mechanism leading to cyclopentannulation. For the benzannulation, it was found that the most likely mechanism in the case of vinylcarbenes is the chromahexatriene route, whereas for phenylcarbenes, the Dötz route via a ketene intermediate is clearly the most favorable. The reactions leading to the cyclopentannulated and benzannulated products are more exothermic with vinylcarbenes than with phenylcarbenes and also more exothermic with alkoxycarbenes than with aminocarbenes. The relative stability of the cyclopentannulated products as compared with the benzannulated products increases for bulkier X substituents and on going from alkoxy‐ to aminocarbenes. The kinetic data concurs with the experimental product distribution found for vinylcarbenes, by which mainly benzannulated products are obtained, and dimethylaminophenylcarbenes, which lead exclusively to cyclopentannulated adducts. 相似文献
110.
Poater J Solà M Bickelhaupt FM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(10):2902-2905
In this response to the preceding paper by Bader, we show that the core arguments and statements presented in the latter are flawed. We argue that it is insufficient for a model of the chemical bond to be rooted in quantum mechanics. A good model must in addition provide insight and possess predictive power. Our molecular orbital (MO) model of the chemical bond, in particular, the associated energy-decomposition approach satisfies all these conditions. On the other hand, Atoms-in-Molecules (AIM) theory is only rooted in quantum mechanics as far as its mathematical framework is concerned. The physical status of its central concepts is not so clear. In particular, "bond paths" and "bond critical points" are once more confirmed not to be indicators of a stabilizing interaction. Moreover, AIM theory lacks any predictive power. We also address specific questions raised in the preceding paper. Finally, interpreting chemical bonding implies choosing a perspective on this phenomenon. That there are many perspectives is a matter of fact and this is in no way unphysical. What is unscientific is to claim uniqueness and truth for one of these choices, namely AIM, and to dismiss on this ground all other approaches. 相似文献