181 research outputs found
Site determination and thermally assisted tunneling in homogenous nucleation
A combined low-temperature scanning tunneling microscopy and density
functional theory study on the binding and diffusion of copper monomers,
dimers, and trimers adsorbed on Cu(111) is presented. Whereas atoms in trimers
are found in fcc sites only, monomers as well as atoms in dimers can occupy the
stable fcc as well as the metastable hcp site. In fact the dimer fcc-hcp
configuration was found to be only 1.3 meV less favorable with respect to the
fcc-fcc configuration. This enables a confined intra-cell dimer motion, which
at temperatures below 5 K is dominated by thermally assisted tunneling.Comment: 4 pages, 4 figure
Structure and binding in crystals of cage-like molecules: hexamine and platonic hydrocarbons
In this paper, we show that first-principle calculations using a van der
Waals density functional (vdW-DF), [Phys. Rev. Lett. , 246401
(2004)] permits determination of molecular crystal structure. We study the
crystal structures of hexamine and the platonic hydrocarbons (cubane and
dodecahedrane). The calculated lattice parameters and cohesion energy agree
well with experiments. Further, we examine the asymptotic accounts of the van
der Waals forces by comparing full vdW-DF with asymptotic atom-based pair
potentials extracted from vdW-DF. The character of the binding differ in the
two cases, with vdW-DF giving a significant enhancement at intermediate and
relevant binding separations. We analyze consequences of this result for
methods such as DFT-D, and question DFT-D's transferability over the full range
of separations
Ab initio structure modeling of complex thin-film oxides: thermodynamical stability of TiC/thin-film alumina
We present an efficient and general method to identify promising candidate
configurations for thin-film oxides and to determine structural characteristics
of (metastable) thin-film structures using ab initio calculations. At the heart
of this method is the complexity of the oxide bulk structure, from which a
large number of thin films with structural building blocks, that is motifs,
from metastable bulk oxide systems can be extracted. These span a coarse but
well-defined network of initial configurations for which density functional
theory (DFT) calculations predict and implement dramatic atomic relaxations in
the corresponding, resulting thin-film candidates. The network of thin-film
candidates (for various film thicknesses and stoichiometries) can be ordered
according to their variation in ab initio total energy or in ab initio
equilibrium Gibbs free energy. Analysis of the relaxed atomic structures for
the most favored structures gives insight into the nature of stable and
metastable thin-film oxides. We investigate ultrathin alumina nucleated on TiC
as a model system to illustrate this method.Comment: Submitted to PRB; 16 pages, 11 figure
Evaluation of New Density Functional with Account of van der Waals Forces by Use of Experimental H2 Physisorption Data on Cu(111)
Detailed experimental data for physisorption potential-energy curves of H2 on
low-indexed faces of Cu challenge theory. Recently, density-functional theory
has been developed to also account for nonlocal correlation effects, including
van der Waals forces. We show that one functional, denoted vdW-DF2, gives a
potential-energy curve promisingly close to the experiment-derived
physisorptionenergy curve. The comparison also gives indications for further
improvements of the functionals
Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks
We develop a proper nonempirical spin-density formalism for the van der Waals density functional (vdW-DF) method. We show that this generalization, termed svdW-DF, is firmly rooted in the single-particle nature of exchange and we test it on a range of spin systems. We investigate in detail the role of spin in the nonlocal correlation driven adsorption of H-2 and CO2 in the linear magnets Mn-MOF74, Fe-MOF74, Co-MOF74, and Ni-MOF74. In all cases, we find that spin plays a significant role during the adsorption process despite the general weakness of the molecular-magnetic responses. The case of CO2 adsorption in Ni-MOF74 is particularly interesting, as the inclusion of spin effects results in an increased attraction, opposite to what the diamagnetic nature of CO2 would suggest. We explain this counterintuitive result, tracking the behavior to a coincidental hybridization of the O p states with the Ni d states in the down-spin channel. More generally, by providing insight on nonlocal correlation in concert with spin effects, our nonempirical svdW-DF method opens the door for a deeper understanding of weak nonlocal magnetic interactions
Nonequilibrium thermodynamics of interacting tunneling transport: variational grand potential, density-functional formulation, and nature of steady-state forces
The standard formulation of tunneling transport rests on an open-boundary
modeling. There, conserving approximations to nonequilibrium Green function or
quantum-statistical mechanics provide consistent but computational costly
approaches; alternatively, use of density-dependent ballistic-transport
calculations [e.g., Phys. Rev. B 52, 5335 (1995)], here denoted `DBT', provide
computationally efficient (approximate) atomistic characterizations of the
electron behavior but has until now lacked a formal justification. This paper
presents an exact, variational nonequilibrium thermodynamic theory for fully
interacting tunneling and provides a rigorous foundation for frozen-nuclei DBT
calculations as a lowest order approximation to an exact nonequilibrium
thermodynamics density functional evaluation. The theory starts from the
complete electron nonequilibrium quantum statistical mechanics and I identify
the operator for the nonequilibrium Gibbs free energy. I demonstrate a minimal
property of a functional for the nonequilibrium thermodynamic grand potential
which thus uniquely identifies the solution as the exact nonequilibrium density
matrix. I also show that a uniqueness-of-density proof from a closely related
study [Phys. Rev. B 78, 165109 (2008)] makes it possible to provide a
single-particle formulation based on universal electron-density functionals. I
illustrate a formal evaluation of the thermodynamics grand potential value
which is closely related to the variation in scattering phase shifts and hence
to Friedel density oscillations. This paper also discusses the difference
between the here-presented exact thermodynamics forces and the often-used
electrostatic forces. Finally the paper documents an inherent adiabatic nature
of the thermodynamics forces and observes that these are suited for a
nonequilibrium implementation of the Born-Oppenheimer approximation.Comment: 37 pages, 3 Figure
Understanding adhesion at as-deposited interfaces from ab initio thermodynamics of deposition growth: thin-film alumina on titanium carbide
We investigate the chemical composition and adhesion of chemical vapour
deposited thin-film alumina on TiC using and extending a recently proposed
nonequilibrium method of ab initio thermodynamics of deposition growth (AIT-DG)
[Rohrer J and Hyldgaard P 2010 Phys. Rev. B 82 045415]. A previous study of
this system [Rohrer J, Ruberto C and Hyldgaard P 2010 J. Phys.: Condens. Matter
22 015004] found that use of equilibrium thermodynamics leads to predictions of
a non-binding TiC/alumina interface, despite the industrial use as a
wear-resistant coating. This discrepancy between equilibrium theory and
experiment is resolved by the AIT-DG method which predicts interfaces with
strong adhesion. The AIT-DG method combines density functional theory
calculations, rate-equation modelling of the pressure evolution of the
deposition environment and thermochemical data. The AIT-DG method was
previously used to predict prevalent terminations of growing or as-deposited
surfaces of binary materials. Here we extent the method to predict surface and
interface compositions of growing or as-deposited thin films on a substrate and
find that inclusion of the nonequilibrium deposition environment has important
implications for the nature of buried interfaces.Comment: 8 pages, 6 figures, submitted to J. Phys.: Condens. Matte
Understanding rapid infant weight gain prevention: a systematic review of quantitative and qualitative evidence.
This is the author accepted manuscriptBACKGROUND: Rapid infant weight gain (RIWG) is strongly related to childhood overweight and obesity, and prevention of RIWG is an approach to early years obesity prevention. This systematic review aimed to explore effectiveness, deliverers' and recipients' experiences of involvement, and key intervention components and processes of such prevention activities. METHODS: Key databases and websites were searched systematically for quantitative and qualitative studies covering intervention effectiveness, experiences with intervention involvement or process outcomes. After duplicate screening and quality assessment, papers were analyzed through narrative synthesis, thematic synthesis and intervention component analysis. RESULTS: Seven quantitative and seven qualitative studies were eligible for inclusion. Most intervention studies reported small, but significant results on infant weight gain. More significant results were measured on weight gain during the first compared with the second year of life. A weak evidence base made elaboration of the relationship between intervention effectiveness and content challenging. Home-delivered interventions may be more relevant for parents. Contextual factors, such as social norms, beliefs and professional identity should be considered during intervention development. Stakeholder involvement can be key to increase intervention acceptability and feasibility. CONCLUSIONS: The field of RIWG prevention is new and evolving, but more research is needed before further conclusions about intervention effectiveness and intervention content can be drawn. Future interventions should take parents, health professionals and other contextual needs into account to improve chances of success. More research on long-term effects on overweight and obesity is needed.UK Clinical Research Collaboratio
Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
We derive the exchange-correlation potential corresponding to the nonlocal
van der Waals density functional [M. Dion, H. Rydberg, E. Schroder, D. C.
Langreth, and B. I. Lundqvist, Phys. Rev. Lett. 92, 246401 (2004)]. We use this
potential for a self-consistent calculation of the ground state properties of a
number of van der Waals complexes as well as crystalline silicon. For the
latter, where little or no van der Waals interaction is expected, we find that
the results are mostly determined by semilocal exchange and correlation as in
standard generalized gradient approximations (GGA), with the fully nonlocal
term giving little effect. On the other hand, our results for the van der Waals
complexes show that the self-consistency has little effect at equilibrium
separations. This finding validates previous calculations with the same
functional that treated the fully nonlocal term as a post GGA perturbation. A
comparison of our results with wave-function calculations demonstrates the
usefulness of our approach. The exchange-correlation potential also allows us
to calculate Hellmann-Feynman forces, hence providing the means for efficient
geometry relaxations as well as unleashing the potential use of other standard
techniques that depend on the self-consistent charge distribution. The nature
of the van der Waals bond is discussed in terms of the self-consistent bonding
charge.Comment: submitted to Phys. Rev.
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