Band renormalization of a polymer physisorbed on graphene investigated by many-body perturbation theory

Many-body perturbation theory at the $G_0W_0$ 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. $G_0W_0$ 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 ∼\sim15 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$\beta$/H$\alpha$ and [\ion{O}{iii}]$\lambda5007$/H$\alpha$ 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 $\mathrm{SB}_\mathrm{H\alpha} = 1.5\times10^{-18}$erg s$^{-1}$ cm$^{-2}$arcsec$^{-2}$. The filaments exhibit unusual low H$\alpha$/H$\beta \approx 2.4$ and low [\ion{O}{iii}]/H$\alpha \sim 0.4 - 0.6$ typical of diffuse ionised gas. They are spectrally narrow ($\sim 20$ km s$^{-1}$) and exhibit no velocity sub-structure. The filaments extend outwards of the elongated \ion{H}{I} halo. On small scales the $N_\mathrm{HI}$ 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

Metalloporphyrins on oxygen-passivated iron: Conformation and order beyond the first layer

On-surface metal porphyrins can undergo electronic and conformational changes that play a crucial role in determining the chemical reactivity of the molecular layer. Therefore, accessing those properties is pivotal for their implementation in organic-based devices. Here, by means of photoemission orbital tomography supported by density functional theory calculations, we investigate the electronic and geometrical structure of two metallated tetraphenyl porphyrins (MTPPs), namely ZnTPP and NiTPP, adsorbed on the oxygen-passivated Fe(100)-p(1 × 1)O surface. Both molecules weakly interact with the surface as no charge transfer is observed. In the case of ZnTPP, our data correspond to those of moderately distorted molecules whereas NiTPP exhibits a severe saddle-shape deformation. From additional experiments on NiTPP multilayer films, we conclude that this distortion is a consequence of the interaction with the substrate, as the NiTPP macrocycle of the second layer turns out to be flat. We further find that distortions in the MTPP macrocycle are accompanied by an increasing energy gap between the highest occupied molecular orbitals (HOMO and HOMO-1). Our results demonstrate that photoemission orbital tomography can simultaneously probe the energy level alignment, the azimuthal orientation, and the adsorption geometry of complex aromatic molecules even in the multilayer regime