524 research outputs found
Linear Dichroism in Resonant Inelastic X-Ray Scattering to Molecular Spin-Orbit States
Polarization-dependent resonant inelastic x-ray scattering (RIXS) is shown to be a new probe of molecular-field effects on the electronic structure of isolated molecules. A combined experimental and theoretical analysis explains the linear dichroism observed in Cl 2p RIXS following Cl 1s excitation in HCl and CF3Cl as due to molecular-field effects, including singlet-triplet exchange, indicating polarized-RIXS provides a direct probe of spin-orbit-state populations applicable to any molecule
Experimental and Theoretical Investigation of Molecular Field Effects by Polarization-resolved Resonant Inelastic X-ray Scattering
We present a combined theoretical and experimental study of molecular field effects on molecular core levels. Polarization-dependent resonant inelastic x-ray scattering is observed experimentally after resonant K-shell excitation of CF3Cl and HCl. We explain the linear dichroism observed in spin-orbit level intensities as due to molecular field effects, including singlet-triplet exchange, and interpret this behavior in terms of population differences in the 2px,y,z inner-shell orbitals. We investigate theoretically the different factors that can affect the electronic populations and the dynamical R dependence of the spin-orbit ratio. Finally, the results obtained are used to interpret the L-shell absorption spectra of the two molecules
Angular and Dynamical Properties in Resonant Inelastic X-ray Scattering: Case Study of Chlorine-containing Molecules
Polarization-dependent resonant inelastic x-ray scattering (RIXS) has been shown to be a probe of molecular-field effects on the electronic structure of isolated molecules. In this experimental analysis we explain the linear dichroism observed in Cl 2p polarized RIXS following Cl 1s excitation of a series of chlorofluoromethanes (CF3Cl, CF2Cl2, CFCl3, and CCl4) as due to molecular-field effects, including singlet-triplet exchange. We present an approach to extract directly the 2p inner-shell electronic state populations from the experimental measurements. Using the angular properties of the measured KV emission we also are able to determine the value of the polarization anisotropy parameter βp for each resolved component of the KV emission spectra
A New Method to Derive Electronegativity from Resonant Inelastic X-ray Scattering
Electronegativity is a well-known property of atoms and substituent groups. Because there is no direct way to measure it, establishing a useful scale for electronegativity often entails correlating it to another chemical parameter; a wide variety of methods have been proposed over the past 80 years to do just that. This work reports a new approach that connects electronegativity to a spectroscopic parameter derived from resonant inelastic x-ray scattering. The new method is demonstrated using a series of chlorine-containing compounds, focusing on the Cl 2p−1LUMO1 electronic states reached after Cl 1s→LUMO core excitation and subsequent KL radiative decay. Based on an electron-density analysis of the LUMOs, the relative weights of the Cl 2pz atomic orbital contributing to the Cl 2p3/2 molecular spin-orbit components are shown to yield a linear electronegativity scale consistent with previous approaches
Adaptive Covariance Estimation with model selection
We provide in this paper a fully adaptive penalized procedure to select a
covariance among a collection of models observing i.i.d replications of the
process at fixed observation points. For this we generalize previous results of
Bigot and al. and propose to use a data driven penalty to obtain an oracle
inequality for the estimator. We prove that this method is an extension to the
matricial regression model of the work by Baraud
Resonant Inelastic X-ray Scattering of Methyl Chloride at the Chlorine K Edge
We present a combined experimental and theoretical study of isolated CH3Cl molecules using resonant inelastic x-ray scattering (RIXS). The high-resolution spectra allow extraction of information about nuclear dynamics in the core-excited molecule. Polarization-resolved RIXS spectra exhibit linear dichroism in the spin-orbit intensities, a result interpreted as due to chemical environment and singlet-triplet exchange in the molecular core levels. From analysis of the polarization-resolved data, Cl 2px, y and 2pz electronic populations can be determined
Femtosecond Nuclear Motion of HCl Probed by Resonant X-ray Raman Scattering in the Cl 1s Region
Femtosecond dynamics are observed by resonant x-ray Raman scattering (RXS) after excitation along the dissociative Cl 1s→6ơ* resonance of gas-phase HCl. The short core-hole lifetime results in a complete breakdown of the common nondispersive behavior of soft-x-ray transitions between parallel potentials. We evidence a general phenomenon of RXS in the hard-x-ray region: a complete quenching of vibrational broadening. This opens up a unique opportunity for superhigh resolution x-ray spectroscopy beyond vibrational and lifetime limitations
AGRI-ENVIRONMENTAL ASSESSMENT OF CONVENTIONAL AND ALTERNATIVE BIOENERGY CROPPING SYSTEMS PROMOTING BIOMASS PRODUCTIVITY
Thomson-resonant Interference Effects in Elastic X-ray Scattering Near the Cl K Edge of HCl
We experimentally observed interference effects in elastic x-ray scattering from gas-phase HCl in the vicinity of the Cl K edge. Comparison to theory identifies these effects as interference effects between non-resonant elastic Thomson scattering and resonant Raman scattering. The results indicate the non-resonant Thomson and resonant Raman contributions are of comparable strength. The measurements also exhibit strong polarization dependence, allowing an easy identification of the resonant and non-resonant contributions
Lithofacies uncertainty modeling in a siliciclastic reservoir setting by incorporating geological contacts and seismic information
Deterministic modeling lonely provides a unique boundary layout, depending on the geological interpretation or interpolation
from the hard available data. Changing the interpreter’s attitude or interpolation parameters leads to displacing the
location of these borders. In contrary, probabilistic modeling of geological domains such as lithofacies is a critical aspect
to providing information to take proper decision in the case of evaluation of oil reservoirs parameters, that is, applicable
for quantification of uncertainty along the boundaries. These stochastic modeling manifests itself dramatically beyond this
occasion. Conventional approaches of probabilistic modeling (object and pixel-based) mostly suffers from consideration
of contact knowledge on the simulated domains. Plurigaussian simulation algorithm, in contrast, allows reproducing the
complex transitions among the lithofacies domains and has found wide acceptance for modeling petroleum reservoirs.
Stationary assumption for this framework has implications on the homogeneous characterization of the lithofacies. In this
case, the proportion is assumed constant and the covariance function as a typical feature of spatial continuity depends only
on the Euclidean distances between two points. But, whenever there exists a heterogeneity phenomenon in the region, this
assumption does not urge model to generate the desired variability of the underlying proportion of facies over the domain.
Geophysical attributes as a secondary variable in this place, plays an important role for generation of the realistic contact
relationship between the simulated categories. In this paper, a hierarchical plurigaussian simulation approach is used to construct
multiple realizations of lithofacies by incorporating the acoustic impedance as soft data through an oil reservoir in Iran.This research was funded by the National Elites Foundation of Iran in collaboration with research Institute Petroleum of Industry in Iran under the project number of 9265005
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