Adsorption of 5-Fluorouracil on Au(111) and Cu(111) surfaces

The adsorption of 5-Fluorouracil (5FU) on Au(111) and Cu(111) surfaces as a function of molecular coverage and temperature has been studied, using x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. The nature of 5-Fluorouracil bonding with the two substrates is remarkably different. The Cu substrate forms a chemisorbed complex with 5-FU while the Au substrate shows only physisorption. NEXAFS data at the C, N and O K-edge show a strong angular dependence, indicating that 5-FU lies nearly parallel on the inert Au(111) surface, and at a steep angle on the Cu(111) surface. 5-FU is a biomolecule used for cancer treatment and the results are relevant for those using metal surfaces to prepare 5-FU for applications such as drug delivery.The adsorption of 5-Fluorouracil (5FU) on Au(111) and Cu(111) surfaces as a function of molecular coverage and temperature has been studied, using x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy. The nature of 5-Fluorouracil bonding with the two substrates is remarkably different. The Cu substrate forms a chemisorbed complex with 5-FU while the Au substrate shows only physisorption. NEXAFS data at the C, N and O K-edge show a strong angular dependence, indicating that 5-FU lies nearly parallel on the inert Au(111) surface, and at a steep angle on the Cu(111) surface. 5-FU is a biomolecule used for cancer treatment and the results are relevant for those using metal surfaces to prepare 5-FU for applications such as drug delivery

Complete determination of molecular orbitals by measurement of phase symmetry and electron density.

Several experimental methods allow measuring the spatial probability density of electrons in atoms, molecules and solids, that is, the absolute square of the respective single-particle wave function. But it is an intrinsic problem of the measurement process that the information about the phase is generally lost during the experiment. The symmetry of this phase, however, is a crucial parameter for the knowledge of the full orbital information in real space. Here, we report on a key experiment that demonstrates that the phase symmetry can be derived from a strictly experimental approach from the circular dichroism in the angular distribution of photoelectrons. In combination with the electron density derived from the same experiment, the full quantum mechanical wave function can thus be determined experimentally

Direct observation of the band gap transition in atomically thin ReS2_2

ReS$_2$ is considered as a promising candidate for novel electronic and sensor applications. The low crystal symmetry of the van der Waals compound ReS$_2$ leads to a highly anisotropic optical, vibrational, and transport behavior. However, the details of the electronic band structure of this fascinating material are still largely unexplored. We present a momentum-resolved study of the electronic structure of monolayer, bilayer, and bulk ReS$_2$ using k-space photoemission microscopy in combination with first-principles calculations. We demonstrate that the valence electrons in bulk ReS$_2$ are - contrary to assumptions in recent literature - significantly delocalized across the van der Waals gap. Furthermore, we directly observe the evolution of the valence band dispersion as a function of the number of layers, revealing a significantly increased effective electron mass in single-layer crystals. We also find that only bilayer ReS$_2$ has a direct band gap. Our results establish bilayer ReS$_2$ as a advantageous building block for two-dimensional devices and van der Waals heterostructures

Signatures of an Atomic Crystal in the Band Structure of a Molecular Thin Film

Transport phenomena in molecular materials are intrinsically linked to the orbital character and the degree of localization of the valence states. Here, we combine angle-resolved photoemission with photoemission tomography to determine the spatial distribution of all molecular states of the valence band structure of a C$_{60}$ thin film. While the two most frontier valence states exhibit a strong band dispersion, the states at larger binding energies are characterized by distinct emission patterns in energy and momentum space. Our findings demonstrate the formation of an atomic crystal-like band structure in a molecular solid with delocalized $\pi$-like valence states and strongly localized $\sigma$-states at larger binding energies

Enhancing electron correlation at a 3D ferromagnetic surface

Spin-resolved momentum microscopy and theoretical calculations are combined beyond the one-electron approximation to unveil the spin-dependent electronic structure of the interface formed between iron (Fe) and an ordered oxygen (O) atomic layer, and an adsorbate-induced enhancement of electronic correlations is found. It is demonstrated that this enhancement is responsible for a drastic narrowing of the Fe d-bands close to the Fermi energy (EF) and a reduction of the exchange splitting, which is not accounted for in the Stoner picture of ferromagnetism. In addition, correlation leads to a significant spin-dependent broadening of the electronic bands at higher binding energies and their merging with satellite features, which are manifestations of a pure many-electron behavior. Overall, adatom adsorption can be used to vary the material parameters of transition metal surfaces to access different intermediate electronic correlated regimes, which will otherwise not be accessible. The results show that the concepts developed to understand the physics and chemistry of adsorbate–metal interfaces, relevant for a variety of research areas, from spintronics to catalysis, need to be reconsidered with many-particle effects being of utmost importance. These may affect chemisorption energy, spin transport, magnetic order, and even play a key role in the emergence of ferromagnetism at interfaces between non-magnetic systems

Valence structures of aromatic bioactive compounds: a combined theoretical and experimental study.

Valence electronic structures of three recently isolated aryl bioactive compounds, namely 2-phenylethanol (2PE), p-hydroxyphenylethanol (HPE) and 4-hydroxybenzaldehyde (HBA), are studied using a combined theoretical and experimental method. Density functional theory-based calculations indicate that the side chains cause electron charge redistribution and therefore influence the aromaticity of the benzene derivatives. The simulated IR spectra further reveal features induced by the side chains. Solvent effects on the IR spectra are simulated using the polarizable continuum model, which exhibits enhancement of the O-H stretch vibrations with significant red-shift of 464 cm(-1) in 2PE. A significant spectral peak splitting of 94 cm(-1) between O(4)-H and O(8)-H of HPE is revealed in an aqueous environment. Experimental measurements for valence binding energy spectra for 2PE, HPE and HBA are presented and analyzed using outer-valence Green function calculations. The experimental (predicted) first ionization energies are measured as 9.19 (8.79), 8.47 (8.27) and 8.97 (8.82) eV for 2PE, HPE and HBA, respectively. The frontier orbitals (highest occupied molecular orbitals, HOMOs, and lowest unoccupied molecular orbitals, LUMOs) have similar atomic orbital characters although the HOMO-LUMO energy gaps are quite different

Twist angle dependent interlayer transfer of valley polarization from excitons to free charge carriers in WSe2_2/MoSe2_2 heterobilayers

We identify an optical excitation mechanism that transfers a valley polarization from photo-excited electron-hole pairs to free charge carriers in twisted WSe$_2$/MoSe$_2$ heterobilayers. For small twist angles, the valley lifetimes of the charge carriers are surprisingly short, despite the occurrence of interlayer excitons with their presumably long recombination and polarization lifetimes. For large twist angles, we measure an increase in both the valley polarization and its respective lifetime by more than two orders of magnitude. Interestingly, in such heterobilayers we observe an interlayer transfer of valley polarization from the WSe$_2$ layer into the MoSe$_2$ layer. This mechanism enables the creation of a photo-induced valley polarization of free charge carriers in MoSe$_2$, which amplitude scales with the gate-induced charge carrier density. This is in contrast to monolayer MoSe$_2$, where such a gate-tunable valley polarization cannot be achieved. By combining time-resolved Kerr rotation, photoluminesence and angle-resolved photoemission spectroscopy measurements with first principles calculations, we show that these findings can be explained by twist angle dependent interlayer scattering mechanisms involving the Q- and $\Gamma$-valleys.Comment: 21 pages, 10 figure

VUV photon induced fluorescence study of SF5CF3

The interaction of SF$_5$CF$_3$ with vacuum-UV radiation has been investigated by photon induced fluorescence spectroscopy. Total fluorescence yield and dispersed fluorescence spectra of SF$_5$CF$_3$ were recorded in the 200-1000 nm fluorescence window. In all cases, the fluorescence spectra resemble those of CF$_3$X (X=H, F, Cl, and Br) molecules. At photon energies below 20 eV, the emission is attributed to the excited CF$_3$ and CF$_2$ fragments. The threshold for the CF$_3$ emission is 10.2 ± 0.2 eV, giving an upper-limit estimate for the SF$_5$-CF$_3$ bond dissociation energy of 3.9 ± 0.3 eV. The excitation functions of the CF3 and CF2 emissions were measured in the photon energy range 13.6 – 27.0 eV. The resonant structures observed in SF$_5$CF$_3$ are attributed to electronic transitions from valence to Rydberg orbitals, following similar assignments in CF$_3$X molecules. The photoabsorption spectrum of SF$_5$CF$_3$ shows features at the same energies, indicating a strong contribution from Rydberg excitations

Electronic band structure changes across the antiferromagnetic phase transition of exfoliated MnPS3_3 probed by μ\mu-ARPES

Exfoliated magnetic 2D materials enable versatile tuning of magnetization, e.g., by gating or providing proximity-induced exchange interaction. However, their electronic band structure after exfoliation has not been probed, most likely due to their photochemical sensitivity. Here, we provide micron-scale angle-resolved photoelectron spectroscopy of the exfoliated intralayer antiferromagnet MnPS$_3$ above and below the N\'{e}el temperature down to one monolayer. The favorable comparison with density functional theory calculations enables to identify the orbital character of the observed bands. Consistently, we find pronounced changes across the N\'{e}el temperature for bands that consist of Mn 3d and 3p levels of adjacent S atoms. The deduced orbital mixture indicates that the superexchange is relevant for the magnetic interaction. There are only minor changes between monolayer and thicker films demonstrating the predominant 2D character of MnPS$_3$. The novel access is transferable to other MPX$_3$ materials (M: transition metal, P: phosphorus, X: chalcogenide) providing a multitude of antiferromagnetic arrangements.Comment: 26 pages, 17 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, understanding those properties is pivotal for the design and implementation of 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(1x1)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, while 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