216 research outputs found
Effect of Pressure on Superconducting Ca-intercalated Graphite CaC
The pressure effect on the superconducting transition temperature () of
the newly-discovered Ca-intercalated graphite compound CaC has been
investigated up to 16 kbar. is found to increase under pressure
with a large relative ratio / of +0.4 %/kbar. Using
first-principles calculations, we show that the large and positive effect of
pressure on can be explained in the scope of electron-phonon theory due
to the presence of a soft phonon branch associated to in-plane vibrations of Ca
atoms. Implications of the present findings on the current debate about the
superconducting mechanism in graphite intercalation compounds are discussed.Comment: 6 pages, 5 figs, final PRB versio
Development of a Classical Force Field for the Oxidised Si Surface: Application to Hydrophilic Wafer Bonding
We have developed a classical two- and three-body interaction potential to
simulate the hydroxylated, natively oxidised Si surface in contact with water
solutions, based on the combination and extension of the Stillinger-Weber
potential and of a potential originally developed to simulate SiO2 polymorphs.
The potential parameters are chosen to reproduce the structure, charge
distribution, tensile surface stress and interactions with single water
molecules of a natively oxidised Si surface model previously obtained by means
of accurate density functional theory simulations. We have applied the
potential to the case of hydrophilic silicon wafer bonding at room temperature,
revealing maximum room temperature work of adhesion values for natively
oxidised and amorphous silica surfaces of 97 mJ/m2 and 90mJ/m2, respectively,
at a water adsorption coverage of approximately 1 monolayer. The difference
arises from the stronger interaction of the natively oxidised surface with
liquid water, resulting in a higher heat of immersion (203 mJ/m2 vs. 166
mJ/m2), and may be explained in terms of the more pronounced water structuring
close to the surface in alternating layers of larger and smaller density with
respect to the liquid bulk. The computed force-displacement bonding curves may
be a useful input for cohesive zone models where both the topographic details
of the surfaces and the dependence of the attractive force on the initial
surface separation and wetting can be taken into account
Data-efficient machine learning for molecular crystal structure prediction
The combination of modern machine learning (ML) approaches with high-quality data from quantum mechanical (QM) calculations can yield models with an unrivalled accuracy/cost ratio. However, such methods are ultimately limited by the computational effort required to produce the reference data. In particular, reference calculations for periodic systems with many atoms can become prohibitively expensive for higher levels of theory. This trade-off is critical in the context of organic crystal structure prediction (CSP). Here, a data-efficient ML approach would be highly desirable, since screening a huge space of possible polymorphs in a narrow energy range requires the assessment of a large number of trial structures with high accuracy. In this contribution, we present tailored Δ-ML models that allow screening a wide range of crystal candidates while adequately describing the subtle interplay between intermolecular interactions such as H-bonding and many-body dispersion effects. This is achieved by enhancing a physics-based description of long-range interactions at the density functional tight binding (DFTB) level—for which an efficient implementation is available—with a short-range ML model trained on high-quality first-principles reference data. The presented workflow is broadly applicable to different molecular materials, without the need for a single periodic calculation at the reference level of theory. We show that this even allows the use of wavefunction methods in CSP
Edge-functionalized and substitutional doped graphene nanoribbons: electronic and spin properties
Graphene nanoribbons are the counterpart of carbon nanotubes in
graphene-based nanoelectronics. We investigate the electronic properties of
chemically modified ribbons by means of density functional theory. We observe
that chemical modifications of zigzag ribbons can break the spin degeneracy.
This promotes the onset of a semiconducting-metal transition, or of an
half-semiconducting state, with the two spin channels having a different
bandgap, or of a spin-polarized half-semiconducting state -where the spins in
the valence and conduction bands are oppositely polarized. Edge
functionalization of armchair ribbons gives electronic states a few eV away
from the Fermi level, and does not significantly affect their bandgap. N and B
produce different effects, depending on the position of the substitutional
site. In particular, edge substitutions at low density do not significantly
alter the bandgap, while bulk substitution promotes the onset of
semiconducting-metal transitions. Pyridine-like defects induce a
semiconducting-metal transition.Comment: 12 pages, 5 figure
Von Zeipel - Lidov - Kozai cycles in action: <i>Kepler</i> triples with eclipse depth variations:KICs 6964043, 5653126, 5731312, and 8023317
Improved tensor-product expansions for the two-particle density matrix
We present a new density-matrix functional within the recently introduced
framework for tensor-product expansions of the two-particle density matrix. It
performs well both for the homogeneous electron gas as well as atoms. For the
homogeneous electron gas, it performs significantly better than all previous
density-matrix functionals, becoming very accurate for high densities and
outperforming Hartree-Fock at metallic valence electron densities. For isolated
atoms and ions, it is on a par with previous density-matrix functionals and
generalized gradient approximations to density-functional theory. We also
present analytic results for the correlation energy in the low density limit of
the free electron gas for a broad class of such functionals.Comment: 4 pages, 2 figure
Critical behavior of a traffic flow model
The Nagel-Schreckenberg traffic flow model shows a transition from a free
flow regime to a jammed regime for increasing car density. The measurement of
the dynamical structure factor offers the chance to observe the evolution of
jams without the necessity to define a car to be jammed or not. Above the
jamming transition the dynamical structure factor exhibits for a given k-value
two maxima corresponding to the separation of the system into the free flow
phase and jammed phase. We obtain from a finite-size scaling analysis of the
smallest jam mode that approaching the transition long range correlations of
the jams occur.Comment: 5 pages, 7 figures, accepted for publication in Physical Review
Presence of Many Stable Nonhomogeneous States in an Inertial Car-Following Model
A new single lane car following model of traffic flow is presented. The model
is inertial and free of collisions. It demonstrates experimentally observed
features of traffic flow such as the existence of three regimes: free,
fluctuative (synchronized) and congested (jammed) flow; bistability of free and
fluctuative states in a certain range of densities, which causes the hysteresis
in transitions between these states; jumps in the density-flux plane in the
fluctuative regime and gradual spatial transition from synchronized to free
flow. Our model suggests that in the fluctuative regime there exist many stable
states with different wavelengths, and that the velocity fluctuations in the
congested flow regime decay approximately according to a power law in time.Comment: 4 pages, 4 figure
The effect of substitution and isomeric imperfection on the photophysical behaviour of p-phenylenevinylene trimers
Spectroscopic and photophysical properties of two p-phenylenevinylene (PV) trimers, 2,5-substituted diheptyl-(p-phenylenevinylene) and di-[(2-ethylhexyl)oxy]-(p-phenylenevinylene), were studied using absorption spectroscopy, fluorescence and laser flash photolysis. The change from alkyl to alkyloxy groups red-shifts the absorption and fluorescence bands. The rate of internal conversion is independent of the substitution, whereas alkyloxy substitution increases the S1Â [rightwards wave arrow]Â T1 intersystem crossing rate by an order of magnitude. The relevance for the behaviour of conjugated PPV polymers is discussed. For diheptyl-PV, a sample having ca. 3% of the cis-configuration was also studied. Comparison between the all-trans and the cis-contaminated samples revealed no significant differences in their photophysical properties.http://www.sciencedirect.com/science/article/B6TFN-4C0TKVG-4/1/bb1be7e4a272bb7910483cae927d04a
CHEMICAL MODIFICATION OF CELLULOSE
Thermolytic degradation of cellulose is dependant on its initial DP, accessibility and on
the method and temperature of the treatment. A limiting DP could be detected in the
depolymerizing reaction. The deteriorating action of aggressive water could be demonstrated.
Quantitative correlation was elaborated concerning the role of accessibility in the reaction
between cellulose and reactive dyestuffs. The role of temperature was cleared up in the
ceIlulose-caustic soda interaction. New bleaching process was elaborated with the use of singlet
oxygen. Physical characteristics, amount of releasable formaldehyde and colouristic influence of
resin finishing of cotton could be optimized
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