429 research outputs found
Tunability of the optical absorption in small silver cluster-polymer hybrid systems
We have calculated the absorption characteristics of different hybrid systems
consisting of Ag, Ag2 or Ag3 atomic clusters and poly(methacrylic acid) (PMAA)
using the time-dependent density-functional theory. The polymer is found to
have an extensive structural-dependency on the spectral patterns of the hybrid
systems relative to the bare clusters. The absorption spectrum can be `tuned'
to the visible range for hybrid systems with an odd number of electrons per
silver cluster, whereas for hybrid systems comprising an even number of
electrons, the leading absorption edge can be shifted up to about 4.5 eV. The
results give theoretical support to the experimental observations on the
absorption in the visible range in metal cluster-polymer hybrid structures.Comment: Updated layout and minor changes in versions 2 and
Energetics of positron states trapped at vacancies in solids
We report a computational first-principles study of positron trapping at
vacancy defects in metals and semiconductors. The main emphasis is on the
energetics of the trapping process including the interplay between the positron
state and the defect's ionic structure and on the ensuing annihilation
characteristics of the trapped state. For vacancies in covalent semiconductors
the ion relaxation is a crucial part of the positron trapping process enabling
the localization of the positron state. However, positron trapping does not
strongly affect the characteristic features of the electronic structure, e.g.,
the ionization levels change only moderately. Also in the case of metal
vacancies the positron-induced ion relaxation has a noticeable effect on the
calculated positron lifetime and momentum distribution of annihilating
electron-positron pairs.Comment: Submitted to Physical Review B on 17 April 2007. Revised version
submitted on 6 July 200
First-principles calculation of positron lifetimes and affinities in perfect and imperfect transition-metal carbides and nitrides
First-principles electronic structure and positron-state calculations for transition-metal carbides and nitrides are performed. Perfect NaCl structures as well as structures with metal or carbon/nitrogen vacancies are considered. The positron affinities and lifetimes are determined. The trends are discussed and the results are compared with recent positron lifetime measurements for group-IV and -V refractory metal carbides. The present analysis suggests, contradictory to an earlier interpretation, that positrons are trapped and annihilated at both carbon and metal vacancies. The concentration of metal vacancies detected by positron annihilation methods is probably very low, below the sensitivity limit of other experimental methods.Peer reviewe
Modeling the momentum distributions of annihilating electron-positron pairs in solids
Measuring the Doppler broadening of the positron annihilation radiation or
the angular correlation between the two annihilation gamma quanta reflects the
momentum distribution of electrons seen by positrons in the
material.Vacancy-type defects in solids localize positrons and the measured
spectra are sensitive to the detailed chemical and geometric environments of
the defects. However, the measured information is indirect and when using it in
defect identification comparisons with theoretically predicted spectra is
indispensable. In this article we present a computational scheme for
calculating momentum distributions of electron-positron pairs annihilating in
solids. Valence electron states and their interaction with ion cores are
described using the all-electron projector augmented-wave method, and atomic
orbitals are used to describe the core states. We apply our numerical scheme to
selected systems and compare three different enhancement (electron-positron
correlation) schemes previously used in the calculation of momentum
distributions of annihilating electron-positron pairs within the
density-functional theory. We show that the use of a state-dependent
enhancement scheme leads to better results than a position-dependent
enhancement factor in the case of ratios of Doppler spectra between different
systems. Further, we demonstrate the applicability of our scheme for studying
vacancy-type defects in metals and semiconductors. Especially we study the
effect of forces due to a positron localized at a vacancy-type defect on the
ionic relaxations.Comment: Submitted to Physical Review B on September 1 2005. Revised
manuscript submitted on November 14 200
Polycyclic aromatic hydrocarbon processing in a hot gas
Context: PAHs are thought to be a ubiquitous and important dust component of
the interstellar medium. However, the effects of their immersion in a hot
(post-shock) gas have never before been fully investigated. Aims: We study the
effects of energetic ion and electron collisions on PAHs in the hot post-shock
gas behind interstellar shock waves. Methods: We calculate the ion-PAH and
electron-PAH nuclear and electronic interactions, above the carbon atom loss
threshold, in H II regions and in the hot post-shock gas, for temperatures
ranging from 10^3 to 10^8 K. Results: PAH destruction is dominated by He
collisions at low temperatures (T < 3x10^4 K), and by electron collisions at
higher temperatures. Smaller PAHs are destroyed faster for T < 10^6 K, but the
destruction rates are roughly the same for all PAHs at higher temperatures. The
PAH lifetime in a tenuous hot gas (n_H ~ 0.01 cm^-3, T ~ 10^7 K), typical of
the coronal gas in galactic outflows, is found to be about thousand years,
orders of magnitude shorter than the typical lifetime of such objects.
Conclusions: In a hot gas, PAHs are principally destroyed by electron
collisions and not by the absorption of X-ray photons from the hot gas. The
resulting erosion of PAHs occurs via C_2 loss from the periphery of the
molecule, thus preserving the aromatic structure. The observation of PAH
emission from a million degree, or more, gas is only possible if the emitting
PAHs are ablated from dense, entrained clumps that have not yet been exposed to
the full effect of the hot gas.Comment: 16 pages, 11 figures, 3 tables, typos corrected and PAH acronym in
the title substituted with full name to match version published in Astronomy
and Astrophysic
Analysis of electron-positron momentum spectra of metallic alloys as supported by first-principles calculations
Electron-positron momentum distributions measured by the coincidence Doppler
broadening method can be used in the chemical analysis of the annihilation
environment, typically a vacancy-impurity complex in a solid. In the present
work, we study possibilities for a quantitative analysis, i.e., for
distinguishing the average numbers of different atomic species around the
defect. First-principles electronic structure calculations self-consistently
determining electron and positron densities and ion positions are performed for
vacancy-solute complexes in Al-Cu, Al-Mg-Cu, and Al-Mg-Cu-Ag alloys. The
ensuing simulated coincidence Doppler broadening spectra are compared with
measured ones for defect identification. A linear fitting procedure, which uses
the spectra for positrons trapped at vacancies in pure constituent metals as
components, has previously been employed to find the relative percentages of
different atomic species around the vacancy [A. Somoza et al. Phys. Rev. B 65,
094107 (2002)]. We test the reliability of the procedure by the help of
first-principles results for vacancy-solute complexes and vacancies in
constituent metals.Comment: Submitted to Physical Review B on September 19 2006. Revised version
submitted on November 8 2006. Published on February 14 200
Excited states of Na nanoislands on the Cu(111) surface
Electronic states of one monolayer high Na nanoislands on the Cu(111) surface are studied as a function of the nanoisland size. Properties of nanoislands such as one-electron states, the electron density, and the associated potential are obtained self-consistently within the density-functional formalism using a one-dimensional pseudopotential for the Cu(111) substrate and the jellium model for Na. A wave packet propagation method is used to study the energies and lifetimes of quasistationary states localized at Na islands. For very large islands, island-localized states merge into the two-dimensional continuum of the Na quantum well state. Thus, we assign the quasistationary states studied as arising from the quantization of the two-dimensional quantum well continuum due to the finite island size. The scattering at the island boundaries results in the energy-conserving resonant electron transfer into the continuum of the substrate states broadening the island-localized states into resonances.Peer reviewe
Broken Symmetry in Density-Functional Theory: Analysis and Cure
We present a detailed analysis of the broken-symmetry mean-field solutions
using a four-electron rectangular quantum dot as a model system. Comparisons of
the density-functional theory predictions with the exact ones show that the
symmetry breaking results from the single-configuration wave function used in
the mean-field approach. As a general cure we present a scheme that
systematically incorporates several configurations into the density-functional
theory and restores the symmetry. This cure is easily applicable to any
density-functional approach.Comment: 4 pages, 4 figures, submitted to PR
Energetics and Vibrational States for Hydrogen on Pt(111)
We present a combination of theoretical calculations and experiments for the
low-lying vibrational excitations of H and D atoms adsorbed on the Pt(111)
surface. The vibrational band states are calculated based on the full
three-dimensional adiabatic potential energy surface obtained from first
principles calculations. For coverages less than three quarters of a monolayer,
the observed experimental high-resolution electron peaks at 31 and 68meV are in
excellent agreement with the theoretical transitions between selected bands.
Our results convincingly demonstrate the need to go beyond the local harmonic
oscillator picture to understand the dynamics of this system.Comment: In press at Phys. Rev. Lett - to appear in April 200
A fourfold coordinated point defect in silicon
Due to their technological importance, point defects in silicon are among the
best studied physical systems. The experimental examination of point defects
buried in bulk is difficult and evidence for the various defects usually
indirect. Simulations of defects in silicon have been performed at various
levels of sophistication ranging from fast force fields to accurate density
functional calculations. The generally accepted viewpoint from all these
studies is that vacancies and self interstitials are the basic point defects in
silicon. We challenge this point of view by presenting density functional
calculations that show that there is a new fourfold coordinated point defect in
silicon that is lower in energy
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