1,040 research outputs found
On the premelting features in sodium clusters
Melting in Na_n clusters described with an empirical embedded-atom potential
has been reexamined in the size range 55<=n<=147 with a special attention at
sizes close to 130. Contrary to previous findings, premelting effects are also
present at such medium sizes, and they turn out to be even stronger than the
melting process itself for Na_133 or Na_135. These results indicate that the
empirical potential is_qualitatively_ unadequate to model sodium clusters.Comment: 4 pages, 3 postscript figure
Theoretical study of the finite temperature spectroscopy in van der Waals clusters. III Solvated Chromophore as an effective diatomics
The absorption spectroscopy of calcium-doped argon clusters is described in
terms of an effective diatomics molecule Ca-(Ar_n), in the framework of
semiclassical vertical transitions. We show how, upon choosing a suitable
reaction coordinate, the effective finite-temperature equilibrium properties
can be obtained for the ground- and excited-surfaces from the potential of mean
force (PMF). An extension of the recent multiple range random-walk method is
used to calculate the PMF over continuous intervals of distances. The
absorption spectra calculated using this single-coordinate description are
found to be in good agreement with the spectra obtained from high-statistics
Monte Carlo data, in various situations. For CaAr, we compare the
performances of two different choices of the reaction coordinate. For CaAr_37,
the method is seen to be accurate enough to distinguish between different
low-energy structures. Finally, the idea of casting the initial many-body
problem into a single degree of freedom problem is tested on the spectroscopy
of calcium in bulk solid argon.Comment: 8 pages, 9 figure
Stacked clusters of polycyclic aromatic hydrocarbon molecules
Clusters of polycyclic aromatic hydrocarbon (PAH) molecules are modelled
using explicit all-atom potentials using a rigid body approximation. The PAH's
considered range from pyrene (C10H8) to circumcoronene (C54H18), and clusters
containing between 2 and 32 molecules are investigated. In addition to the
usual repulsion-dispersion interactions, electrostatic point-charge
interactions are incorporated, as obtained from density functional theory
calculations. The general electrostatic distribution in neutral or singly
charged PAH's is reproduced well using a fluctuating charges analysis, which
provides an adequate description of the multipolar distribution. Global
optimization is performed using a variety of methods, including basin-hopping
and parallel tempering Monte Carlo. We find evidence that stacking the PAH
molecules generally yields the most stable motif. A structural transition
between one-dimensional stacks and three-dimensional shapes built from mutiple
stacks is observed at larger sizes, and the threshold for this transition
increases with the size of the monomer. Larger aggregates seem to evolve toward
the packing observed for benzene in bulk.Difficulties met in optimizing these
clusters are analysed in terms of the strong anisotropy of the molecules. We
also discuss segregation in heterogeneous clusters and vibrational properties
in the context of astrophysical observations.Comment: 12 pages, 7 figure
Theoretical study of finite temperature spectroscopy in van der Waals clusters. II Time-dependent absorption spectra
Using approximate partition functions and a master equation approach, we
investigate the statistical relaxation toward equilibrium in selected CaAr
clusters. The Gaussian theory of absorption (previous article) is employed to
calculate the average photoabsorption intensity associated with the 4s^2->
4s^14p^1 transition of calcium as a function of time during relaxation. In
CaAr_6 and CaAr_10 simple relaxation is observed with a single time scale.
CaAr_13 exhibits much slower dynamics and the relaxation occurs over two
distinct time scales. CaAr_37 shows much slower relaxation with multiple
transients, reminiscent of glassy behavior due to competition between different
low-energy structures. We interpret these results in terms of the underlying
potential energy surfaces for these clusters.Comment: 10 pages, 9 figure
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A New Parameterization of Hydrous Mantle Melting
Modeling of melt formation and transport in all tectonic settings requires the inclusion of water, since water has large effects on mantle solidi as well as physical properties of liquids. To facilitate the inclusion of water in melting models this paper presents a new parameterization for melt fraction as a function of pressure, temperature, water content and modal cpx, based on knowledge gained from recent advances in the fields of thermodynamic modeling as well as experimental investigations of peridotite melting and hydrous equilibria. The parameterization is computationally efficient and can be modified easily as better experimental data become available. We compare it to other published parameterizations and test it insimple calculations of adiabatic decompression melting (mid-ocean ridge) and hydrous melting (subduction zone).Earth and Planetary Science
Wetting to Non-wetting Transition in Sodium-Coated C_60
Based on ab initi and density-functional theory calculations, an empirical
potential is proposed to model the interaction between a fullerene molecule and
many sodium atoms. This model predicts homogeneous coverage of C_60 below 8 Na
atoms, and a progressive droplet formation above this size. The effects of
ionization, temperature, and external electric field indicate that the various,
and apparently contradictory, experimental results can indeed be put into
agreement.Comment: 4 pages, 4 postscript figure
Size effect in the ionization energy of PAH clusters
We report the first experimental measurement of the near-threshold
photo-ionization spectra of polycyclic aromatic hydrocarbon clusters made of
pyrene C16H10 and coronene C24H12, obtained using imaging photoelectron
photoion coincidence spectrometry with a VUV synchrotron beamline. The
experimental results of the ionization energy are confronted to calculated ones
obtained from simulations using dedicated electronic structure treatment for
large ionized molecular clusters. Experiment and theory consistently find a
decrease of the ionization energy with cluster size. The inclusion of
temperature effects in the simulations leads to a lowering of this energy and
to a quantitative agreement with the experiment. In the case of pyrene, both
theory and experiment show a discontinuity in the IE trend for the hexamer
Theoretical study of finite temperature spectroscopy in van der Waals clusters. I. Probing phase changes in CaAr_n
The photoabsorption spectra of calcium-doped argon clusters CaAr_n are
investigated at thermal equilibrium using a variety of theoretical and
numerical tools. The influence of temperature on the absorption spectra is
estimated using the quantum superposition method for a variety of cluster sizes
in the range 6<=n<=146. At the harmonic level of approximation, the absorption
intensity is calculated through an extension of the Gaussian theory by Wadi and
Pollak [J. Chem. Phys. vol 110, 11890 (1999)]. This theory is tested on simple,
few-atom systems in both the classical and quantum regimes for which highly
accurate Monte Carlo data can be obtained. By incorporating quantum anharmonic
corrections to the partition functions and respective weights of the isomers,
we show that the superposition method can correctly describe the
finite-temperature spectroscopic properties of CaAr_n systems. The use of the
absorption spectrum as a possible probe of isomerization or phase changes in
the argon cluster is discussed at the light of finite-size effects.Comment: 17 pages, 9 figure
Exchange Monte Carlo for Molecular Simulations with Monoelectronic Hamiltonians
We introduce a general Monte Carlo scheme for achieving atomistic simulations
with monoelectronic Hamiltonians including the thermalization of both nuclear
and electronic degrees of freedom. The kinetic Monte Carlo algorithm is used to
obtain the exact occupation numbers of the electronic levels at canonical
equilibrium, and comparison is made with Fermi-Dirac statistics in infinite and
finite systems. The effects of a nonzero electronic temperature on the
thermodynamic properties of liquid silver and sodium clusters are presented
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