67 research outputs found
Theory for the Ultrafast Structural Response of optically excited small clusters: Time-dependence of the Ionization Potential
Combining an electronic theory with molecular dynamics simulations we present
results for the ultrafast structural changes in small clusters. We determine
the time scale for the change from the linear to a triangular structure after
the photodetachment process Ag. We show that the
time-dependent change of the ionization potential reflects in detail the
internal degrees of freedom, in particular coherent and incoherent motion, and
that it is sensitive to the initial temperature. We compare with experiment and
point out the general significance of our results.Comment: 10 pages, Revtex, 3 postscript figure
Nonradiative Electronic Deexcitation Time Scales in Metal Clusters
The life-times due to Auger-electron emission for a hole on a deep electronic
shell of neutral and charged sodium clusters are studied for different sizes.
We consider spherical clusters and calculate the Auger-transition probabilities
using the energy levels and wave functions calculated in the
Local-Density-Approximation (LDA).
We obtain that Auger emission processes are energetically not allowed for
neutral and positively charged sodium clusters. In general, the Auger
probabilities in small Na clusters are remarkably different from the
atomic ones and exhibit a rich size dependence.
The Auger decay times of most of the cluster sizes studied are orders of
magnitude larger than in atoms and might be comparable with typical
fragmentation times.Comment: 11 pages, 4 figures. Accepted for publication in Phys. Rev.
Structure and Magnetism of Neutral and Anionic Palladium Clusters
The properties of neutral and anionic Pd_N clusters were investigated with
spin-density-functional calculations. The ground state structures are
three-dimensional for N>3 and they are magnetic with a spin-triplet for 2<=N<=7
and a spin nonet for N=13 neutral clusters. Structural- and spin-isomers were
determined and an anomalous increase of the magnetic moment with temperature is
predicted for a Pd_7 ensemble. Vertical electron detachment and ionization
energies were calculated and the former agree well with measured values for
anionic Pd_N clusters.Comment: 5 pages, 3 figures, fig. 2 in color, accepted to Phys. Rev. Lett.
(2001
Al13H−: Hydrogen atom site selectivity and the shell model
Using a combination of anion photoelectron spectroscopy and density functional theory calculations, we explored the influence of the shell model on H atom site selectivity in Al13H−. Photoelectron spectra revealed that Al13H− has two anionic isomers and for both of them provided vertical detachment energies (VDEs). Theoretical calculations found that the structures of these anionic isomers differ by the position of the hydrogen atom. In one, the hydrogen atom is radially bonded, while in the other, hydrogen caps a triangular face. VDEs for both anionic isomers as well as other energetic relationships were also calculated. Comparison of the measured versus calculated VDE values permitted the structure of each isomer to be confirmed and correlated with its observed photoelectron spectrum. Shell model, electron-counting considerations correctly predicted the relative stabilities of the anionic isomers and identified the stable structure of neutral Al13H
Noncollinear magnetic ordering in small Chromium Clusters
We investigate noncollinear effects in antiferromagnetically coupled clusters
using the general, rotationally invariant form of local spin-density theory.
The coupling to the electronic degrees of freedom is treated with relativistic
non-local pseudopotentials and the ionic structure is optimized by Monte-Carlo
techniques. We find that small chromium clusters (N \le 13) strongly favor
noncollinear configurations of their local magnetic moments due to frustration.
This effect is associated with a significantly lower total magnetization of the
noncollinear ground states, ameliorating the disagreement between Stern-Gerlach
measurements and previous collinear calculations for Cr_{12} and Cr_{13}. Our
results further suggest that the trend to noncollinear configurations might be
a feature common to most antiferromagnetic clusters.Comment: 9 pages, RevTeX plus .eps/.ps figure
Adsorption of CO on a Platinum (111) surface - a study within a four-component relativistic density functional approach
We report on results of a theoretical study of the adsorption process of a
single carbon oxide molecule on a Platinum (111) surface. A four-component
relativistic density functional method was applied to account for a proper
description of the strong relativistic effects. A limited number of atoms in
the framework of a cluster approach is used to describe the surface. Different
adsorption sites are investigated. We found that CO is preferably adsorbed at
the top position.Comment: 23 Pages with 4 figure
Insights into the geometries, electronic and magnetic properties of neutral and charged palladium clusters
We performed an unbiased structure search for low-lying energetic minima of neutral and charged palladium Pd(n)(Q) (n = 2–20, Q = 0, + 1 and –1) clusters using CALYPSO method in combination with density functional theory (DFT) calculations. The main candidates for the lowest energy neutral, cationic and anionic clusters are identified, and several new candidate structures for the cationic and anionic ground states are obtained. It is found that the ground state structures of small palladium clusters are more sensitive to the charge states. For the medium size Pd(n)(0/+/–) (n = 16–20) clusters, a fcc-like growth behavior is found. The structural transition from bilayer-like structures to cage-like structures is likely to occur at n = 14 for the neutral and cationic clusters. In contrast, for the anionic counterparts, the structural transition occurs at Pd(13)(–). The photoelectron spectra (PES) of palladium clusters are simulated based on the time-dependent density functional theory (TD-DFT) method and compared with the experimental data. The good agreement between the experimental PES and simulated spectra provides us unequivocal structural information to fully solve the global minimum structures, allowing for new molecular insights into the chemical interactions in the Pd cages
Production of large metallocarbohedrene clusters using a pulsed arc cluster ion source
The hypothesis of the existence of multi-cage structures of metallocarbohedrene
clusters ("metcars" ) bases on the observation of certain magic numbers in the
mass spectra corresponding to an excess of carbon atoms with respect to the bulk
stochiometry (1:1 for TiC). E.g., the appearance of the magic number cluster
Ti13C22 has been explained by assuming a double-cage structure. However, the
same magic number can be assigned to a cube (= Ti13C14) with 8
additional carbon atoms forming carbon dimers at the corners of the cube. We
recorded mass spectra of TinCm clusters using a pulsed arc cluster ion source
with an additional annealing discharge. For the positive ions, Ti8C is the
major peak in the mass spectrum. For the anions, much larger clusters could be
generated. The maxima of the larger TinC clusters including Ti13C are
located at masses slightly above the fcc cubic shell closings. The shift can be
explained by the bonding of additional C atoms at the corners of the cubes
Electronic structure of small fullerenes : evidence for the high stability of C32
The electronic structure of small fullerenes determined experimentally by anion photoelectron spectroscopy is compared with calculations. A huge mass signal and a large gap of 1.3 eV comparable to the gap of C70 have been found for C32, indicating that this cluster is the most stable fullerene below C60. Also C36, C44, and C50 exhibit large gaps and surprisingly high stabilities. The criteria for the selection of clusters sufficiently stable to form a cluster material are discussed
- …