200 research outputs found
Ab initio density functional investigation of B_24 cluster: Rings, Tubes, Planes, and Cages
We investigate the equilibrium geometries and the systematics of bonding in
various isomers of a 24-atom boron cluster using Born-Oppenheimer molecular
dynamics within the framework of density functional theory. The isomers studied
are the rings, the convex and the quasiplanar structures, the tubes and, the
closed structures. A staggered double-ring is found to be the most stable
structure amongst the isomers studied. Our calculations reveal that a 24-atom
boron cluster does form closed 3-d structures. All isomers show staggered
arrangement of nearest neighbor atoms. Such a staggering facilitates
hybridization in boron cluster. A polarization of bonds between the peripheral
atoms in the ring and the planar isomers is also seen. Finally, we discuss the
fusion of two boron icosahedra. We find that the fusion occurs when the
distance between the two icosahedra is less than a critical distance of about
6.5a.u.Comment: 8 pages, 9 figures in jpeg format Editorially approved for
publication in Phys. Rev.
Broad boron sheets and boron nanotubes: An ab initio study of structural, electronic, and mechanical properties
Based on a numerical ab initio study, we discuss a structure model for a
broad boron sheet, which is the analog of a single graphite sheet, and the
precursor of boron nanotubes. The sheet has linear chains of sp hybridized
sigma bonds lying only along its armchair direction, a high stiffness, and
anisotropic bonds properties. The puckering of the sheet is explained as a
mechanism to stabilize the sp sigma bonds. The anisotropic bond properties of
the boron sheet lead to a two-dimensional reference lattice structure, which is
rectangular rather than triangular. As a consequence the chiral angles of
related boron nanotubes range from 0 to 90 degrees. Given the electronic
properties of the boron sheets, we demonstrate that all of the related boron
nanotubes are metallic, irrespective of their radius and chiral angle, and we
also postulate the existence of helical currents in ideal chiral nanotubes.
Furthermore, we show that the strain energy of boron nanotubes will depend on
their radii, as well as on their chiral angles. This is a rather unique
property among nanotubular systems, and it could be the basis of a different
type of structure control within nanotechnology.Comment: 16 pages, 17 figures, 2 tables, Versions: v1=preview, v2=first final,
v3=minor corrections, v4=document slightly reworke
Ab initio prediction of Boron compounds arising from Borozene: Structural and electronic properties
Structure and electronic properties of two unusual boron clusters obtained by
fusion of borozene rings has been studied by means of first principles
calculations, based on the generalized-gradient approximation of the density
functional theory, and the semiempirical tight-binding method was used for the
transport calculations. The role of disorder has also been considered with
single vacancies and substitutional atoms. Results show that the pure boron
clusters are topologically planar and characterized by (3c-2e) bonds, which can
explain, together with the aromaticity (estimated by means of NICS), the
remarkable cohesive energy values obtained. Such feature makes these systems
competitive with the most stable boron clusters to date. On the contrary, the
introduction of impurities compromises stability and planarity in both cases.
The energy gap values indicate that these clusters possess a semiconducting
character, while when the larger system is considered, zero-values of the
density of states are found exclusively within the HOMO-LUMO gap. Electron
transport calculations within the Landauer formalism confirm these indications,
showing semiconductor-like low bias differential conductance for these
stuctures. Differences and similarities with Carbon clusters are highlighted in
the discussion.Comment: 10 pages, 2 tables, 5 figure
Boron Fullerenes: A First-Principles Study
A family of unusually stable boron cages was identified and examined using
first-principles local density functional method. The structure of the
fullerenes is similar to that of the B12 icosahedron and consists of six
crossing double-rings. The energetically most stable fullerene is made up of
180 boron atoms. A connection between the fullerene family and its precursors,
boron sheets, is made. We show that the most stable boron sheets are not
necessarily precursors of very stable boron cages. Our finding is a step
forward in the understanding of the structure of the recently produced boron
nanotubes.Comment: 10 pages, 4 figures, 1 tabl
Finite-size and correlation-induced effects in Mean-field Dynamics
The brain's activity is characterized by the interaction of a very large
number of neurons that are strongly affected by noise. However, signals often
arise at macroscopic scales integrating the effect of many neurons into a
reliable pattern of activity. In order to study such large neuronal assemblies,
one is often led to derive mean-field limits summarizing the effect of the
interaction of a large number of neurons into an effective signal. Classical
mean-field approaches consider the evolution of a deterministic variable, the
mean activity, thus neglecting the stochastic nature of neural behavior. In
this article, we build upon two recent approaches that include correlations and
higher order moments in mean-field equations, and study how these stochastic
effects influence the solutions of the mean-field equations, both in the limit
of an infinite number of neurons and for large yet finite networks. We
introduce a new model, the infinite model, which arises from both equations by
a rescaling of the variables and, which is invertible for finite-size networks,
and hence, provides equivalent equations to those previously derived models.
The study of this model allows us to understand qualitative behavior of such
large-scale networks. We show that, though the solutions of the deterministic
mean-field equation constitute uncorrelated solutions of the new mean-field
equations, the stability properties of limit cycles are modified by the
presence of correlations, and additional non-trivial behaviors including
periodic orbits appear when there were none in the mean field. The origin of
all these behaviors is then explored in finite-size networks where interesting
mesoscopic scale effects appear. This study leads us to show that the
infinite-size system appears as a singular limit of the network equations, and
for any finite network, the system will differ from the infinite system
Optical absorption in boron clusters B and B : A first principles configuration interaction approach
The linear optical absorption spectra in neutral boron cluster B and
cationic B are calculated using a first principles correlated
electron approach. The geometries of several low-lying isomers of these
clusters were optimized at the coupled-cluster singles doubles (CCSD) level of
theory. With these optimized ground-state geometries, excited states of
different isomers were computed using the singles configuration-interaction
(SCI) approach. The many body wavefunctions of various excited states have been
analysed and the nature of optical excitation involved are found to be of
collective, plasmonic type.Comment: 22 pages, 38 figures. An invited article submitted to European
Physical Journal D. This work was presented in the International Symposium on
Small Particles and Inorganic Clusters - XVI, held in Leuven, Belgiu
Structure and properties of small sodium clusters
We have investigated structure and properties of small metal clusters using
all-electron ab initio theoretical methods based on the Hartree-Fock
approximation and density functional theory, perturbation theory and compared
results of our calculations with the available experimental data and the
results of other theoretical works. We have systematically calculated the
optimized geometries of neutral and singly charged sodium clusters having up to
20 atoms, their multipole moments (dipole and quadrupole), static
polarizabilities, binding energies per atom, ionization potentials and
frequencies of normal vibration modes. Our calculations demonstrate the great
role of many-electron correlations in the formation of electronic and ionic
structure of small metal clusters and form a good basis for further detailed
study of their dynamic properties, as well as structure and properties of other
atomic cluster systems.Comment: 47 pages, 16 figure
Synthesis and in-depth studies on the anticancer activity of novel palladacyclopentadienyl complexes stabilized by N-Heterocyclic carbene ligands
New palladacyclopentadienyl complexes with bis-N-heterocyclic carbenes as spectator ligands have been synthesized and exhaustively characterized. The crystal structure of complex 1a has been also determined by X-ray diffraction analysis. Their in vitro cytotoxicity and that of other palladacyclopentadienyl derivatives coordinating different ancillary ligands has been determined against different cancer cell lines. Many complexes have shown an antiproliferative activity toward tumor cells often definitely better than cisplatin, whereas they have resulted practically inactive against the non-cancer MRC-5 cell line. The mechanism of action of bis-NHC derivative 1a, particularly active against ovarian cancer cell lines was studied in depth. Through a longitudinally analysis, it is shown that compound 1a induces apoptosis via DNA damage and release of cytochrome C. We propose compound 1a as a powerful and specific drug for the therapy of a deadly disease such as high grade serous ovarian cancer
A Real-Space Full Multigrid study of the fragmentation of Li11+ clusters
We have studied the fragmentation of Li11+ clusters into the two
experimentally observed products (Li9+,Li2) and (Li10+,Li) The ground state
structures for the two fragmentation channels are found by Molecular Dynamics
Simulated Annealing in the framework of Local Density Functional theory.
Energetics considerations suggest that the fragmentation process is dominated
by non-equilibrium processes. We use a real-space approach to solve the
Kohn-Sham problem, where the Laplacian operator is discretized according to the
Mehrstellen scheme, and take advantage of a Full MultiGrid (FMG) strategy to
accelerate convergence. When applied to isolated clusters we find our FMG
method to be more efficient than state-of-the-art plane wave calculations.Comment: 9 pages + 6 Figures (in gzipped tar file
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