150 research outputs found
Adsorption and dissociation of molecular oxygen on the (0001) surface of double hexagonal close packed americium
In our continuing attempts to understand theoretically various surface
properties such as corrosion and potential catalytic activity of actinide
surfaces in the presence of environmental gases, we report here the first ab
initio study of molecular adsorption on the double hexagonal packed (dhcp)
americium (0001) surface. Dissociative adsorption is found to be energetically
more favorable compared to molecular adsorption. The most stable configuration
corresponds to a horizontal approach molecular dissociation with the oxygen
atoms occupying neighboring h3 sites, with chemisorption energies at the NSOC
and SOC theoretical levels being 9.395 eV and 9.886 eV, respectively. The
corresponding distances of the oxygen molecule from the surface and
oxygen-oxygen distance were found to be 0.953 Ang. and 3.731 Ang.,
respectively. Overall our calculations indicate that chemisorption energies in
cases with SOC are slightly more stable than the cases with NSOC in the
0.089-0.493 eV range. The work functions and net magnetic moments respectively
increased and decreased in all cases compared with the corresponding quantities
of the bare dhcp Am (0001) surface. The adsorbate-substrate interactions have
been analyzed in detail using the partial charges inside the muffin-tin
spheres, difference charge density distributions, and the local density of
states. The effects, if any, of chemisorption on the Am 5f electron
localization-delocalization characteristics in the vicinity of the Fermi level
are also discussed.Comment: 6 tables, 10 figure
A Density Functional Study of Atomic Hydrogen and Oxygen Chemisorption on the Relaxed (0001) Surface of Double Hexagonal Close Packed Americium
Ab initio total energy calculations within the framework of density
functional theory have been performed for atomic hydrogen and oxygen
chemisorption on the (0001) surface of double hexagonal packed americium using
a full-potential all-electron linearized augmented plane wave plus local
orbitals method. Chemisorption energies were optimized with respect to the
distance of the adatom from the relaxed surface for three adsorption sites,
namely top, bridge, and hollow hcp sites, the adlayer structure corresponding
to coverage of a 0.25 monolayer in all cases. Chemisorption energies were
computed at the scalar-relativistic level (no spin-orbit coupling NSOC) and at
the fully relativistic level (with spin-orbit coupling SOC). The two-fold
bridge adsorption site was found to be the most stable site for O at both the
NSOC and SOC theoretical levels with chemisorption energies of 8.204 eV and
8.368 eV respectively, while the three-fold hollow hcp adsorption site was
found to be the most stable site for H with chemisorption energies of 3.136 eV
at the NSOC level and 3.217 eV at the SOC level. The respective distances of
the H and O adatoms from the surface were found to be 1.196 Ang. and 1.164 Ang.
Overall our calculations indicate that chemisorption energies in cases with SOC
are slightly more stable than the cases with NSOC in the 0.049-0.238 eV range.
The work functions and net magnetic moments respectively increased and
decreased in all cases compared with the corresponding quantities of bare dhcp
Am (0001) surface. The partial charges inside the muffin-tins, difference
charge density distributions, and the local density of states have been used to
analyze the Am-adatom bond interactions in detail. The implications of
chemisorption on Am 5f electron localization-delocalization are also discussed.Comment: 9 Tables, 5 figure
Defects and lithium migration in Li<sub>2</sub>CuO<sub>2</sub>
Li2CuO2 is an important candidate material as a cathode in lithium ion batteries. Atomistic simulation methods are used to investigate the defect processes, electronic structure and lithium migration mechanisms in Li2CuO2. Here we show that the lithium energy of migration via the vacancy mechanism is very low, at 0.11 eV. The high lithium Frenkel energy (1.88 eV/defect) prompted the consideration of defect engineering strategies in order to increase the concentration of lithium vacancies that act as vehicles for the vacancy mediated lithium self-diffusion in Li2CuO2. It is shown that aluminium doping will significantly reduce the energy required to form a lithium vacancy from 1.88 eV to 0.97 eV for every aluminium introduced, however, it will also increase the migration energy barrier of lithium in the vicinity of the aluminium dopant to 0.22 eV. Still, the introduction of aluminium is favourable compared to the lithium Frenkel process. Other trivalent dopants considered herein require significantly higher solution energies, whereas their impact on the migration energy barrier was more pronounced. When considering the electronic structure of defective Li2CuO2, the presence of aluminium dopants results in the introduction of electronic states into the energy band gap. Therefore, doping with aluminium is an effective doping strategy to increase the concentration of lithium vacancies, with a minimal impact on the kinetics
Impact of uniaxial strain and doping on oxygen diffusion in CeO2
Doped ceria is an important electrolyte for solid oxide fuel cell applications. Molecular dynamics simulations have been used to investigate the impact of uniaxial strain along the directions and rare-earth doping (Yb, Er, Ho, Dy, Gd, Sm, Nd, and La) on oxygen diffusion. We introduce a new potential model that is able to describe the thermal expansion and elastic properties of ceria to give excellent agreement with experimental data. We calculate the activation energy of oxygen migration in the temperature range 900-1900K for both unstrained and rare-earth doped ceria systems under tensile strain. Uniaxial strain has a considerable effect in lowering the activation energies of oxygen migration. A more pronounced increase in oxygen diffusivities is predicted at the lower end of the temperature range for all the dopants considered
Incipient equilibrium conditions for methane hydrate formation in aqueous mixed electrolyte solutions
Bibliography: p. 57-64
Exploring the Ring-Opening Pathways in the Reaction of Morpholinyl Radicals with Oxygen Molecule
Quantum chemistry calculations using hybrid density functional
theory and the coupled-cluster method have been performed to investigate
the ring-opening pathways in the oxidation of morpholine (1-oxa-4-aza-cyclohexane).
Hydrogen abstraction can form two different carbon-centered radicals,
morpholin-2-yl or morpholin-3-yl, or the nitrogen-centered radical,
morpholin-4-yl, none of which are found to have low-energy pathways
to ring-opening. Extensive exploration of multiple reaction pathways
following molecular oxygen addition to these three radicals revealed
two competitive low energy pathways to ring-opening. Addition of O<sub>2</sub> to either carbon-centered radical, followed by a 1,4-H shifting
mechanism can yield a long-lived cyclic epoxy intermediate, susceptible
to ring-opening, following further radical attack. In particular,
the second pathway begins with O<sub>2</sub> attack on morpholin-2-yl,
followed by a 1,5-H shift and a unimolecular ring-opening without
having to overcome a high barrier, releasing a significant amount
of heat in the overall ring-opening reaction. The calculations provide
valuable context for the development of mechanisms for the low temperature
combustion chemistry of nitrogen and oxygen-containing fuels
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