41 research outputs found
A new technique for the sp/sp characterisation of carbon materials
We present a technique to determine the sp/sp ratio of carbon
materials which is based on the electron energy-loss spectroscopy and which
uses the theoretical spectrum of graphite obtained from ab initio electronic
structure calculations. The method relies on the separation of the and
components of the carbon K-edge of graphite. This spectrum
is adopted and assumed to be transferable to other carbon systems given an
appropriate parametrisation of the broadening. The method is applied on a
series of Monte-Carlo generated amorphous carbon structures and is shown to be
stable over a wide range of the energy windows for which spectral integration
is performed. The results are found to be in good agreement with the sp
fraction obtained from a microscopic scheme which uses the orbital axis
vector (POAV1) analysis. The technique was also applied on a series of
experimental spectra of amorphous carbon and was found to be in good agreement
with the results obtained from a functional fitting approach.Comment: 5 pages, 4 figures, two tables revtex4, Submitted for publication to
Phys. Rev. Let
The Partial Averaging method
The partial averaging technique is defined and used in conjunction with the
random series implementation of the Feynman-Kac formula. It enjoys certain
properties such as good rates of convergence and convergence for potentials
with coulombic singularities. In this work, I introduce the reader to the
technique and I analyze the basic mathematical properties of the method. I show
that the method is convergent for all Kato-class potentials that have finite
Gaussian transform.Comment: 9 pages, no figures; one reference correcte
Delocalization and the semiclassical description of molecular rotation
We discuss phase-space delocalization for the rigid rotator within a
semiclassical context by recourse to the Husimi distributions of both the
linear and the anisotropic instances. Our treatment is based upon the
concomitant Fisher information measures. The pertinent Wehrl entropy is also
investigated in the linear case.Comment: 6 pages, 3 figure
Pulling absorbing and collapsing polymers from a surface
A self-interacting polymer with one end attached to a sticky surface has been
studied by means of a flat-histogram stochastic growth algorithm known as
FlatPERM. We examined the four-dimensional parameter space of the number of
monomers up to 91, self-attraction, surface attraction and force applied to an
end of the polymer. Using this powerful algorithm the \emph{complete} parameter
space of interactions and force has been considered. Recently it has been
conjectured that a hierarchy of states appears at low temperature/poor solvent
conditions where a polymer exists in a finite number of layers close to a
surface. We find re-entrant behaviour from a stretched phase into these
layering phases when an appropriate force is applied to the polymer. We also
find that, contrary to what may be expected, the polymer desorbs from the
surface when a sufficiently strong critical force is applied and does
\emph{not} transcend through either a series of de-layering transitions or
monomer-by-monomer transitions.Comment: 4 pages, 4 figure
Free energy of the Fr\"ohlich polaron in two and three dimensions
We present a novel Path Integral Monte Carlo scheme to solve the Fr\"ohlich
polaron model. At intermediate and strong electron-phonon coupling, the polaron
self-trapping is properly taken into account at the level of an effective
action obtained by a preaveraging procedure with a retarded trial action. We
compute the free energy at several couplings and temperatures in three and two
dimensions. Our results show that the accuracy of the Feynman variational upper
bound for the free energy is always better than 5% although the thermodynamics
derived from it is not correct. Our estimates of the ground state energies
demonstrate that the second cumulant correction to the variational upper bound
predicts the self energy to better than 1% at intermediate and strong coupling.Comment: RevTeX 7 pages 3 figures, revised versio
Density functional theory calculations of the carbon ELNES of small diameter armchair and zigzag nanotubes: core-hole, curvature and momentum transfer orientation effects
We perform density functional theory calculations on a series of armchair and
zigzag nanotubes of diameters less than 1nm using the all-electron
Full-Potential(-Linearised)-Augmented-Plane-Wave (FPLAPW) method. Emphasis is
laid on the effects of curvature, the electron beam orientation and the
inclusion of the core-hole on the carbon electron energy loss K-edge. The
electron energy loss near-edge spectra of all the studied tubes show strong
curvature effects compared to that of flat graphene. The curvature induced
hybridisation is shown to have a more drastic effect on the
electronic properties of zigzag tubes than on those of armchair tubes. We show
that the core-hole effect must be accounted for in order to correctly reproduce
electron energy loss measurements. We also find that, the energy loss near edge
spectra of these carbon systems are dominantly dipole selected and that they
can be expressed simply as a proportionality with the local momentum projected
density of states, thus portraying the weak energy dependence of the transition
matrix elements. Compared to graphite, the ELNES of carbon nanotubes show a
reduced anisotropy.Comment: 25 pages, 15 figures, revtex4 submitted for publication to Phys. Rev.
The effect of Pt NPs crystallinity and distribution on the photocatalytic activity of Pt-g-C<sub>3</sub>N<sub>4</sub>
We thank EPSRC for support through the EPSRC/NSF chemistry programme and the Royal Society for a Wolfson Merit award.Loading of a co-catalyst on the surface of a semiconductor photocatalyst is often carried out without considering the effect of the loading procedure on the final product. The present study looks in detail at the effect that the loading method has on the morphology and final composition of platinum-based nanoparticles by means of XPS and TEM analysis. Additionally, reduction pre-treatments are performed to investigate how the coverage, crystallinity and composition of the NPs affect the photocatalytic H2 evolution. The activity of Pt–g-C3N4 can significantly be enhanced by controlling the properties of the co-catalyst NPs.Publisher PDFPeer reviewe
Random Series and Discrete Path Integral methods: The Levy-Ciesielski implementation
We perform a thorough analysis of the relationship between discrete and
series representation path integral methods, which are the main numerical
techniques used in connection with the Feynman-Kac formula. First, a new
interpretation of the so-called standard discrete path integral methods is
derived by direct discretization of the Feynman-Kac formula. Second, we
consider a particular random series technique based upon the Levy-Ciesielski
representation of the Brownian bridge and analyze its main implementations,
namely the primitive, the partial averaging, and the reweighted versions. It is
shown that the n=2^k-1 subsequence of each of these methods can also be
interpreted as a discrete path integral method with appropriate short-time
approximations. We therefore establish a direct connection between the discrete
and the random series approaches. In the end, we give sharp estimates on the
rates of convergence of the partial averaging and the reweighted
Levy-Ciesielski random series approach for sufficiently smooth potentials. The
asymptotic rates of convergence are found to be O(1/n^2), in agreement with the
rates of convergence of the best standard discrete path integral techniques.Comment: 20 pages, 4 figures; the two equations before Eq. 14 are corrected;
other typos are remove
Ab initio calculations of optical properties of silver clusters: cross-over from molecular to nanoscale behavior
Electronic and optical properties of silver clusters were calculated using
two different \textit{ab initio} approaches: 1) based on all-electron
full-potential linearized-augmented plane-wave method and 2) local basis
function pseudopotential approach. Agreement is found between the two methods
for small and intermediate sized clusters for which the former method is
limited due to its all-electron formulation. The latter, due to non-periodic
boundary conditions, is the more natural approach to simulate small clusters.
The effect of cluster size is then explored using the local basis function
approach. We find that as the cluster size increases, the electronic structure
undergoes a transition from molecular behavior to nanoparticle behavior at a
cluster size of 140 atoms (diameter \,nm). Above this cluster size
the step-like electronic structure, evident as several features in the
imaginary part of the polarizability of all clusters smaller than
Ag, gives way to a dominant plasmon peak localized at
wavelengths 350\,nm 600\,nm. It is, thus, at this length-scale
that the conduction electrons' collective oscillations that are responsible for
plasmonic resonances begin to dominate the opto-electronic properties of silver
nanoclusters