157 research outputs found
Band renormalization of a polymer physisorbed on graphene investigated by many-body perturbation theory
Many-body perturbation theory at the level is employed to study the
electronic properties of poly(\emph{para}-phenylene) (PPP) on graphene.
Analysis of the charge density and the electrostatic potential shows that the
polymer-surface interaction gives rise to the formation of only weak surface
dipoles with no charge transfer between the polymer and the surface. In the
local-density approximation (LDA) of density-functional theory, the band
structure of the combined system appears as a superposition of the eigenstates
of its constituents. Consequently, the LDA band gap of PPP remains unchanged
upon adsorption onto graphene. calculations, however, renormalize the
electronic levels of the weakly physisorbed polymer. Thereby, its band gap is
considerably reduced compared to that of the isolated PPP chain. This effect
can be understood in terms of image charges induced in the graphene layer,
which allows us to explain the quasi-particle gap of PPP versus
polymer-graphene distance by applying a classical image-potential model. For
distances below 4.5 {\AA}, however, deviations from this simple classical model
arise which we qualitatively explain by taking into account the polarizablity
of the adsorbate. For a quantitative description with predictive power,
however, we emphasize the need for an accurate ab-initio description of the
electronic structure for weakly coupled systems at equilibrium bonding
distances.Comment: 9 pages, 11 figure
Interchain interaction and Davydov splitting in polythiophene crystals: An ab initio approach
The crystal-induced energy splitting of the lowest excitonic state in polymer crystals, the so-called Davydov splitting Δ, is calculated with a first-principles density-matrix scheme. We show that different crystalline arrangements lead to significant variations in Δ, from below to above the thermal energy kBT at room temperature, with relevant implications on the luminescence efficiency. This is one more piece of evidence supporting the fact that control of interchain interactions and solid-state packing is essential for the design of efficient optical devices
Insight into intramolecular chemical structure modifications by on-surface reaction using photoemission tomography
The sensitivity of photoemission tomography (PT) to directly probe single molecule on-surface intramolecular reactions will be shown here. PT application in the study of molecules possessing peripheral ligands and structural flexibility is tested on the temperature-induced dehydrogenation intramolecular reaction on Ag(100), leading from CoOEP to the final product CoTBP. Along with the ring-closure reaction, the electronic occupancy and energy level alignment of the frontier orbitals, as well as the oxidation state of the metal ion, are elucidated for both the CoOEP and CoTBP systems
Geometry-Dependent Electronic Properties of Highly Fluorescent Conjugated Molecules
URL:http://link.aps.org/doi/10.1103/PhysRevLett.85.2388
DOI:10.1103/PhysRevLett.85.2388We present a combined experimental/theoretical study of the electronic properties of conjugated para- phenylene type molecules under high pressure up to 80 kbar. Pressure is used as a tool to vary the molecular geometry and intermolecular interaction. The influence of the latter two on singlet and triplet excitons as well as polarons is monitored via optical spectroscopy. We have performed band structure calculations for the planar poly(para-phenylene) and calculated the dielectric function. By varying the intermolecular distances and the length of the polymer repeat unit the observed pressure effects can be explained.Supported by the University of Missouri Research Board, OeNB Project No. 6608, the vector-computer facilities at the University of Graz
Stacking-Fault Energy and Anti-Invar Effect in FeMn Alloys
Based on state-of-the-art density-functional-theory methods we calculate the
stacking-fault energy of the paramagnetic random Fe-22.5at.%Mn alloy between
300-800 K. We estimate magnetic thermal excitations by considering longitudinal
spin-fluctuations. Our results demonstrate that the interplay between the
magnetic excitations and the thermal lattice expansion is the main factor
determining the anti-Invar effect, the hcp-fcc transformation temperature, and
the stacking-fault energy, which is in excellent agreement with measurements.Comment: 5 pages, 3 figure
Non-adiabatic and time-resolved photoelectron spectroscopy for molecular systems
We quantify the non-adiabatic contributions to the vibronic sidebands of
equilibrium and explicitly time-resolved non-equilibrium photoelectron spectra
for a vibronic model system of Trans-Polyacetylene. Using exact
diagonalization, we directly evaluate the sum-over-states expressions for the
linear-response photocurrent. We show that spurious peaks appear in the
Born-Oppenheimer approximation for the vibronic spectral function, which are
not present in the exact spectral function of the system. The effect can be
traced back to the factorized nature of the Born-Oppenheimer initial and final
photoemission states and also persists when either only initial, or final
states are replaced by correlated vibronic states. Only when correlated initial
and final vibronic states are taken into account, the spurious spectral weights
of the Born-Oppenheimer approximation are suppressed. In the non-equilibrium
case, we illustrate for an initial Franck-Condon excitation and an explicit
pump-pulse excitation how the vibronic wavepacket motion of the system can be
traced in the time-resolved photoelectron spectra as function of the pump-probe
delay
Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO2 Exposure
Due to its unique magnetic properties offered by the open-shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d-states of FePc and the sp-band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The FeII ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO2 dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO2 at room temperature
A 15 kpc outflow cone piercing through the halo of the blue compact metal-poor galaxy SBS0335-052
Context: Outflows from low-mass star-forming galaxies are a fundamental
ingredient for models of galaxy evolution and cosmology.
Aims: The onset of kpc-scale ionised filaments in the halo of the metal-poor
compact dwarf SBS 0335-052E was previously not linked to an outflow. We here we
investigate whether these filaments provide evidence for an outflow.
Methods: We obtained new VLT/MUSE WFM and deep NRAO/VLA B-configuration 21cm
data of the galaxy. The MUSE data provide morphology, kinematics, and emission
line ratios H/H and [\ion{O}{iii}]/H of the
low surface-brightness filaments, while the VLA data deliver morphology and
kinematics of the neutral gas in and around the system. Both datasets are used
in concert for comparisons between the ionised and the neutral phase.
Results: We report the prolongation of a lacy filamentary ionised structure
up to a projected distance of 16 kpc at erg s cmarcsec. The filaments exhibit
unusual low H/H and low [\ion{O}{iii}]/H typical of diffuse ionised gas. They are spectrally narrow ( km s) and exhibit no velocity sub-structure. The filaments extend
outwards of the elongated \ion{H}{I} halo. On small scales the
peak is offset from the main star-forming sites. Morphology and kinematics of
\ion{H}{I} and \ion{H}{II} reveal how star-formation driven feedback interacts
differently with the ionised and the neutral phase.
Conclusions: We reason that the filaments are a large scale manifestation of
star-formation driven feedback, namely limb-brightened edges of a giant outflow
cone that protrudes through the halo of this gas-rich system. A simple toy
model of such a conical-structure is found to be commensurable with the
observations.Comment: Accepted version in A&A after language editing. 22 pages, 24 figure
Towards ensemble asteroseismology of the young open clusters Chi Persei and NGC 6910
As a result of the variability survey in Chi Persei and NGC6910, the number
of Beta Cep stars that are members of these two open clusters is increased to
twenty stars, nine in NGC6910 and eleven in Chi Persei. We compare pulsational
properties, in particular the frequency spectra, of Beta Cep stars in both
clusters and explain the differences in terms of the global parameters of the
clusters. We also indicate that the more complicated pattern of the variability
among B type stars in Chi Persei is very likely caused by higher rotational
velocities of stars in this cluster. We conclude that the sample of pulsating
stars in the two open clusters constitutes a very good starting point for the
ensemble asteroseismology of Beta Cep-type stars and maybe also for other
B-type pulsators.Comment: 4 pages, Astronomische Nachrichten, HELAS IV Conference, Arecife,
Lanzarote, Feb 2010, submitte
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