146 research outputs found
Experimental and quantum chemical studies of a novel synthetic prenylated chalcone
BACKGROUND: Chalcones are ubiquitous natural compounds with a wide variety of reported biological activities, including antitumoral, antiviral and antimicrobial effects. Furthermore, chalcones are being studied for its potential use in organic electroluminescent devices; therefore the description of their spectroscopic properties is important to elucidate the structure of these molecules. One of the main techniques available for structure elucidation is the use of Nuclear Magnetic Resonance Spectroscopy (NMR). Accordingly, the prediction of the NMR spectra in this kind of molecules is necessary to gather information about the influence of substituents on their spectra. RESULTS: A novel substituted chalcone has been synthetized. In order to identify the functional groups present in the new synthesized compound and confirm its chemical structure, experimental and theoretical (1)H-NMR and (13)C-NMR spectra were analyzed. The theoretical molecular structure and NMR spectra were calculated at both the Hartree-Fock and Density Functional (meta: TPSS; hybrid: B3LYP and PBE1PBE; hybrid meta GGA: M05-2X and M06-2X) levels of theory in combination with a 6-311++G(d,p) basis set. The structural parameters showed that the best method for geometry optimization was DFT:M06-2X/6-311++G(d,p), whereas the calculated bond angles and bond distances match experimental values of similar chalcone derivatives. The NMR calculations were carried out using the Gauge-Independent Atomic Orbital (GIAO) formalism in a DFT:M06-2X/6-311++G(d,p) optimized geometry. CONCLUSION: Considering all HF and DFT methods with GIAO calculations, TPSS and PBE1PBE were the most accurate methods used for calculation of (1)H-NMR and (13)C-NMR chemical shifts, which was almost similar to the B3LYP functional, followed in order by HF, M05-2X and M06-2X methods. All calculations were done using the Gaussian 09 software package. Theoretical calculations can be used to predict and confirm the structure of substituted chalcones with good correlation with the experimental data
A large-scale R-matrix calculation for electron-impact excitation of the Ne O-like ion
The five J levels within a or ground state complex provide
an excellent testing ground for the comparison of theoretical line ratios with
astrophysically observed values, in addition to providing valuable electron
temperature and density diagnostics. The low temperature nature of the line
ratios ensure that the theoretically derived values are sensitive to the
underlying atomic structure and electron-impact excitation rates. Previous
R-matrix calculations for the Ne O-like ion exhibit large spurious
structure in the cross sections at higher electron energies, which may affect
Maxwellian averaged rates even at low temperatures. Furthermore, there is an
absence of comprehensive excitation data between the excited states that may
provide newer diagnostics to compliment the more established lines discussed in
this paper. To resolve these issues, we present both a small scale 56-level
Breit-Pauli (BP) calculation and a large-scale 554 levels R-matrix Intermediate
Coupling Frame Transformation (ICFT) calculation that extends the scope and
validity of earlier JAJOM calculations both in terms of the atomic structure
and scattering cross sections. Our results provide a comprehensive
electron-impact excitation data set for all transitions to higher shells.
The fundamental atomic data for this O-like ion is subsequently used within a
collisional radiative framework to provide the line ratios across a range of
electron temperatures and densities of interest in astrophysical observations.Comment: 17 pages, 8 figure
Electron recombination with multicharged ions via chaotic many-electron states
We show that a dense spectrum of chaotic multiply-excited eigenstates can
play a major role in collision processes involving many-electron multicharged
ions. A statistical theory based on chaotic properties of the eigenstates
enables one to obtain relevant energy-averaged cross sections in terms of sums
over single-electron orbitals. Our calculation of the low-energy electron
recombination of Au shows that the resonant process is 200 times more
intense than direct radiative recombination, which explains the recent
experimental results of Hoffknecht {\em et al.} [J. Phys. B {\bf 31}, 2415
(1998)].Comment: 9 pages, including 1 figure, REVTe
Interference effects in the photorecombination of argonlike Sc3+ ions: Storage-ring experiment and theory
Absolute total electron-ion recombination rate coefficients of argonlike
Sc3+(3s2 3p6) ions have been measured for relative energies between electrons
and ions ranging from 0 to 45 eV. This energy range comprises all dielectronic
recombination resonances attached to 3p -> 3d and 3p -> 4s excitations. A broad
resonance with an experimental width of 0.89 +- 0.07 eV due to the 3p5 3d2 2F
intermediate state is found at 12.31 +- 0.03 eV with a small experimental
evidence for an asymmetric line shape. From R-Matrix and perturbative
calculations we infer that the asymmetric line shape may not only be due to
quantum mechanical interference between direct and resonant recombination
channels as predicted by Gorczyca et al. [Phys. Rev. A 56, 4742 (1997)], but
may partly also be due to the interaction with an adjacent overlapping DR
resonance of the same symmetry. The overall agreement between theory and
experiment is poor. Differences between our experimental and our theoretical
resonance positions are as large as 1.4 eV. This illustrates the difficulty to
accurately describe the structure of an atomic system with an open 3d-shell
with state-of-the-art theoretical methods. Furthermore, we find that a
relativistic theoretical treatment of the system under study is mandatory since
the existence of experimentally observed strong 3p5 3d2 2D and 3p5 3d 4s 2D
resonances can only be explained when calculations beyond LS-coupling are
carried out.Comment: 11 pages, 7 figures, 3 tables, Phys. Rev. A (in print), see also:
http://www.strz.uni-giessen.de/~k
Radiative recombination of bare Bi83+: Experiment versus theory
Electron-ion recombination of completely stripped Bi83+ was investigated at
the Experimental Storage Ring (ESR) of the GSI in Darmstadt. It was the first
experiment of this kind with a bare ion heavier than argon. Absolute
recombination rate coefficients have been measured for relative energies
between ions and electrons from 0 up to about 125 eV. In the energy range from
15 meV to 125 eV a very good agreement is found between the experimental result
and theory for radiative recombination (RR). However, below 15 meV the
experimental rate increasingly exceeds the RR calculation and at Erel = 0 eV it
is a factor of 5.2 above the expected value. For further investigation of this
enhancement phenomenon the electron density in the interaction region was set
to 1.6E6/cm3, 3.2E6/cm3 and 4.7E6/cm3. This variation had no significant
influence on the recombination rate. An additional variation of the magnetic
guiding field of the electrons from 70 mT to 150 mT in steps of 1 mT resulted
in periodic oscillations of the rate which are accompanied by considerable
changes of the transverse electron temperature.Comment: 12 pages, 14 figures, to be published in Phys. Rev. A, see also
http://www.gsi.de/ap/ and http://www.strz.uni-giessen.de/~k
Dielectronic recombination data for dynamic finite-density plasmas I. Goals and methodology
A programme is outlined for the assembly of a comprehensive dielectronic
recombination database within the generalized collisional--radiative (GCR)
framework. It is valid for modelling ions of elements in dynamic finite-density
plasmas such as occur in transient astrophysical plasmas such as solar flares
and in the divertors and high transport regions of magnetic fusion devices. The
resolution and precision of the data are tuned to spectral analysis and so are
sufficient for prediction of the dielectronic recombination contributions to
individual spectral line emissivities. The fundamental data are structured
according to the format prescriptions of the Atomic Data and Analysis Structure
(ADAS) and the production of relevant GCR derived data for application is
described and implemented following ADAS. The requirements on the dielectronic
recombination database are reviewed and the new data are placed in context and
evaluated with respect to older and more approximate treatments. Illustrative
results validate the new high-resolution zero-density dielectronic
recombination data in comparison with measurements made in heavy-ion storage
rings utilizing an electron cooler. We also exemplify the role of the
dielectronic data on GCR coefficient behaviour for some representative light
and medium weight elements.Comment: 14 Pages, 9 Figures. Submitted to Astronomy & Astrophysics April 12,
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Computational molecular characterization of the flavonoid rutin
In this work, we make use of a model chemistry within Density Functional Theory (DFT) recently presented, which is called M05-2X, to calculate the molecular structure of the flavonoid Rutin, as well as to predict the infrared (IR) and ultraviolet (UV-Vis) spectra, the dipole moment and polarizability, the free energy of solvation in different solvents as an indication of solubility, the HOMO and LUMO orbitals, and the chemical reactivity parameters that arise from Conceptual DFT. The calculated values are compared with the available experimental data for this molecule as a means of validation of the used model chemistry
Not So Lucky Any More: CEO Compensation in Financially Distressed Firms
There is a debate on whether executive pay reflects rent extraction due to managerial power or is the result of arms-length bargaining in a principal-agent framework. In this paper we offer a test of the managerial power hypothesis by empirically examining the CEO compensation of U.S. public companies that were ever in financial distress between 1992 and 2005. Using a bias-corrected matching estimator that estimates the causal effects of financial distress, we find that, for the distressed firms, CEO turnover rates increase markedly and their CEOs, both incumbents and successors, experience significant reductions in total compensation. The bulk of the reduction in total compensation derives from the decline in value of stock option grants, which we argue is due to a change in the opportunistic timing of option grants. We define lucky grants as those with grant prices below or at the lowest stock price of the grant month, and we find that the proportion of lucky grants for financially distressed firms is higher before insolvency and lower upon and after insolvency, while the proportion for similar but solvent firms remains stable throughout the period. We interpret this evidence as consistent with a decrease in managerial power induced by a tightening in the outrage constraint due to the episode of financial distress
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