Strain dependence of bonding and hybridization across the metal-insulator transition of VO2

Soft x-ray spectroscopy is used to investigate the strain dependence of the metal-insulator transition of VO2. Changes in the strength of the V 3d - O 2p hybridization are observed across the transition, and are linked to the structural distortion. Furthermore, although the V-V dimerization is well-described by dynamical mean-field theory, the V-O hybridization is found to have an unexpectedly strong dependence on strain that is not predicted by band theory, emphasizing the relevance of the O ion to the physics of VO2

Electric-octupole and pure-electric-quadrupole effects in soft-x-ray photoemission

Second-order [O(k^2), k=omega/c] nondipole effects in soft-x-ray photoemission are demonstrated via an experimental and theoretical study of angular distributions of neon valence photoelectrons in the 100--1200 eV photon-energy range. A newly derived theoretical expression for nondipolar angular distributions characterizes the second-order effects using four new parameters with primary contributions from pure-quadrupole and octupole-dipole interference terms. Independent-particle calculations of these parameters account for a significant portion of the existing discrepancy between experiment and theory for Ne 2p first-order nondipole parameters.Comment: 4 pages, 3 figure

Electronic Structure of the ID Conductor K0.3MoO3 studied using resonant inelastic x-ray scattering and soft x-ray emission spectroscopy

The electronic structure of the quasi-one dimensional conductor K{sub 0.3}MoO{sub 3} has been measured using high resolution resonant inelastic x-ray scattering and x-ray absorption spectroscopy. The data is compared to that from the related two dimensional insulator {alpha}-MoO{sub 3}. Scattering features are observed from both oxides that are explained in terms of the band momentum selectivity of the scattering process, allowing a comparison of the scattering data to recent band structure calculations

Soft systems methodology: a context within a 50-year retrospective of OR/MS

Soft systems methodology (SSM) has been used in the practice of operations research and management science OR/MS) since the early 1970s. In the 1990s, it emerged as a viable academic discipline. Unfortunately, its proponents consider SSM and traditional systems thinking to be mutually exclusive. Despite the differences claimed by SSM proponents between the two, they have been complementary. An extensive sampling of the OR/MS literature over its entire lifetime demonstrates the richness with which the non-SSM literature has been addressing the very same issues as does SSM

Breakdown of the Independent Particle Approximation in High-Energy Photoionization

The independent particle approximation is shown to break down for the photoionization of both inner and outer nℓ (ℓ\u3e0) electrons of all atoms, at high enough energy, owing to interchannel interactions with the nearby ns photoionization channels. The effect is illustrated for Ne 2p in the 1 keV photon energy range through a comparison of theory and experiment. The implications for x-ray photoelectron spectroscopy of molecules and condensed matter are discussed

Cymantrene–Triazole "Click" Products: Structural Characterization and Electrochemical Properties

We report the first known examples of triazole-derivatized cymantrene complexes (η5-[4-substituted triazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I), obtained via a “click” chemical synthesis, bearing a phenyl, 3-aminophenyl, or 4-aminophenyl moiety at the 4-position of the triazole ring. Structural characterization data using multinuclear NMR, UV–vis, ATR-IR, and mass spectrometric methods are provided, as well as crystallographic data for (η5-[4-phenyltriazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I) and (η5-[4-(3-aminophenyl)triazol-1-yl]cyclopentadienyl)tricarbonylmanganese(I). Cyclic voltammetric characterization of the redox behavior of each of the three cymantrene–triazole complexes is presented together with digital simulations, in situ infrared spectroelectrochemistry, and DFT calculations to extract the associated kinetic and thermodynamic parameters. The trypanocidal activity of each cymantrene–triazole complex is also examined, and these complexes are found to be more active than cymantrene alone

Quantum chemical calculations of X-ray emission spectroscopy

The calculation of X-ray emission spectroscopy with equation of motion coupled cluster theory (EOM-CCSD), time dependent density functional theory (TDDFT) and resolution of the identity single excitation configuration interaction with second order perturbation theory (RI-CIS(D)) is studied. These methods can be applied to calculate X-ray emission transitions by using a reference determinant with a core-hole, and they provide a convenient approach to compute the X-ray emission spectroscopy of large systems since all of the required states can be obtained within a single calculation removing the need to perform a separate calculation for each state. For all of the methods, basis sets with the inclusion of additional basis functions to describe core orbitals are necessary, particularly when studying transitions involving the 1s or- bitals of heavier nuclei. EOM-CCSD predicts accurate transition energies when compared with experiment, however, its application to larger systems is restricted by its computational cost and difficulty in converging the CCSD equations for a core-hole reference determinant, which become increasing problematic as the size of the system studied increases. While RI-CIS(D) gives accurate transition energies for small molecules containing first row nuclei, its application to larger systems is limited by the CIS states providing a poor zeroth order reference for perturbation theory which leads to very large errors in the computed transition energies for some states. TDDFT with standard exchange-correlation functionals predicts transition energies that are much larger than experiment. Optimization of a hybrid and short-range cor- rected functional to predict the X-ray emission transitions results in much closer agreement with EOM-CCSD. The most accurate exchange-correlation functional identified is a modified B3LYP hybrid functional with 66% Hartree-Fock exchange, denoted B66LYP, which predicts X-ray emission spectra for a range of molecules including fluorobenzene, nitrobenzene, ace- tone, dimethyl sulfoxide and CF3Cl in good agreement with experiment