151 research outputs found
Density-functional embedding using a plane-wave basis
The constrained electron density method of embedding a Kohn-Sham system in a
substrate system (first described by P. Cortona, Phys. Rev. B {\bf 44}, 8454
(1991) and T.A. Wesolowski and A. Warshel, J. Phys. Chem {\bf 97}, 8050 (1993))
is applied with a plane-wave basis and both local and non-local
pseudopotentials. This method divides the electron density of the system into
substrate and embedded electron densities, the sum of which is the electron
density of the system of interest. Coupling between the substrate and embedded
systems is achieved via approximate kinetic energy functionals. Bulk aluminium
is examined as a test case for which there is a strong interaction between the
substrate and embedded systems. A number of approximations to the
kinetic-energy functional, both semi-local and non-local, are investigated. It
is found that Kohn-Sham results can be well reproduced using a non-local
kinetic energy functional, with the total energy accurate to better than 0.1 eV
per atom and good agreement between the electron densities.Comment: 11 pages, 4 figure
The High-Acceptance Dielectron Spectrometer HADES
HADES is a versatile magnetic spectrometer aimed at studying dielectron
production in pion, proton and heavy-ion induced collisions. Its main features
include a ring imaging gas Cherenkov detector for electron-hadron
discrimination, a tracking system consisting of a set of 6 superconducting
coils producing a toroidal field and drift chambers and a multiplicity and
electron trigger array for additional electron-hadron discrimination and event
characterization. A two-stage trigger system enhances events containing
electrons. The physics program is focused on the investigation of hadron
properties in nuclei and in the hot and dense hadronic matter. The detector
system is characterized by an 85% azimuthal coverage over a polar angle
interval from 18 to 85 degree, a single electron efficiency of 50% and a vector
meson mass resolution of 2.5%. Identification of pions, kaons and protons is
achieved combining time-of-flight and energy loss measurements over a large
momentum range. This paper describes the main features and the performance of
the detector system
Epoxide as a precursor to secondary organic aerosol formation from isoprene photooxidation in the presence of nitrogen oxides
Isoprene is a substantial contributor to the global secondary organic aerosol (SOA) burden, with implications for public health and the climate system. The mechanism by which isoprene-derived SOA is formed and the influence of environmental conditions, however, remain unclear. We present evidence from controlled smog chamber experiments and field measurements that in the presence of high levels of nitrogen oxides (NOx = NO + NO2) typical of urban atmospheres, 2-methyloxirane-2-carboxylic acid (methacrylic acid epoxide, MAE) is a precursor to known isoprene-derived SOA tracers, and ultimately to SOA. We propose that MAE arises from decomposition of the OH adduct of methacryloylperoxynitrate (MPAN). This hypothesis is supported by the similarity of SOA constituents derived from MAE to those from photooxidation of isoprene, methacrolein, and MPAN under high-NOx conditions. Strong support is further derived from computational chemistry calculations and Community Multiscale Air Quality model simulations, yielding predictions consistent with field observations. Field measurements taken in Chapel Hill, North Carolina, considered along with the modeling results indicate the atmospheric significance and relevance of MAE chemistry across the United States, especially in urban areas heavily impacted by isoprene emissions. Identification of MAE implies a major role of atmospheric epoxides in forming SOA from isoprene photooxidation. Updating current atmospheric modeling frameworks with MAE chemistry could improve the way that SOA has been attributed to isoprene based on ambient tracer measurements, and lead to SOA parameterizations that better capture the dependency of yield on NOx
Successful management of multiple permanent pacemaker complications – infection, 13 year old silent lead perforation and exteriorisation following failed percutaneous extraction, superior vena cava obstruction, tricuspid valve endocarditis, pulmonary embolism and prosthetic tricuspid valve thrombosis
A 59 year old man underwent mechanical tricuspid valve replacement and removal of pacemaker generator along with 4 pacemaker leads for pacemaker endocarditis and superior vena cava obstruction after an earlier percutaneous extraction had to be abandoned, 13 years ago, due to cardiac arrest, accompanied by silent, unsuspected right atrial perforation and exteriorisation of lead. Postoperative course was complicated by tricuspid valve thrombosis and secondary pulmonary embolism requiring TPA thrombolysis which was instantly successful. A review of literature of pacemaker endocarditis and tricuspid thrombosis along with the relevant management strategies is presented. We believe this case report is unusual on account of non operative management of right atrial lead perforation following an unsuccessful attempt at percutaneous removal of right sided infected pacemaker leads and the incidental discovery of the perforated lead 13 years later at sternotomy, presentation of pacemaker endocarditis with a massive load of vegetations along the entire pacemaker lead tract in superior vena cava, right atrial endocardium, tricuspid valve and right ventricular endocardium, leading to a functional and structural SVC obstruction, requirement of an unusually large dose of warfarin postoperatively occasioned, in all probability, by antibiotic drug interactions, presentation of tricuspid prosthetic valve thrombosis uniquely as vasovagal syncope and isolated hypoxia and near instantaneous resolution of tricuspid prosthetic valve thrombosis with Alteplase thrombolysis
Reorganization Energy for Internal Electron Transfer in Multicopper Oxidases.
We have calculated the reorganization energy for the intramolecular electron transfer between the reduced type 1 copper site and the peroxy intermediate of the trinuclear cluster in the multicopper oxidase CueO. The calculations are performed at the combined quantum mechanics and molecular mechanics (QM/MM) level, based on molecular dynamics simulations with tailored potentials for the two copper sites. We obtain a reorganization energy of 91-133 kJ/mol, depending on the theoretical treatment. The two Cu sites contribute by 12 and 22 kJ/mol to this energy, whereas the solvent contribution is 34 kJ/mol. The rest comes from the protein, involving small contributions from many residues. We have also estimated the energy difference between the two electron-transfer states and show that the reduction of the peroxy intermediate is exergonic by 43-87 kJ/mol, depending on the theoretical method. Both the solvent and the protein contribute to this energy difference, especially charged residues close to the two Cu sites. We compare these estimates with energies obtained from QM/MM optimizations and QM calculations in a vacuum and discuss differences between the results obtained at various levels of theory
Pentacycloundecane lactam vs lactone norstatine type protease HIV inhibitors: binding energy calculations and DFT study
Eerste hulp bij ongevallen: vier voordrachten voor cadetten van het oudste studiejaar [aan de] Kon. Militaire Academie, Breda
Density-functional-theory calculations of static dipole polarizability of some ions of interest in Mössbauer spectroscopy
Using a hydrodynamic formulation of Kohn-Sham orbital density-functional theory, static dipole polarizabilities αd are calculated for Cr+, Mn2+, Fe3+, Co4+, Ni5+ (3d5 series); Cu+, Zn2+, and Ga3+ (3d10 series); Ru3+(4d5); Sn2+(5s2); and Eu2+(4f7). The calculated αd values are found to be in good agreement with other available theoretical results of comparable accuracy
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