No Arabic abstract
The electronic structure of ZnPc, from sub-monolayers to thick films, on bare and iodated Pt(111) is studied by means of X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS) and scanning tunneling microscopy (STM). Our results suggest that at low coverage ZnPc lies almost parallel to the Pt(111) substrate, in a non-planar configuration induced by Zn-Pt attraction, leading to an inhomogeneous charge distribution within the molecule and charge transfer to the molecule. ZnPc does not form a complete monolayer on the Pt surface, due to a surface-mediated intermolecular repulsion. At higher coverage ZnPc adopts a tilted geometry, due to a reduced molecule-substrate interaction. Our photoemission results illustrate that ZnPc is practically decoupled from Pt, already from the second layer. Pre-deposition of iodine on Pt hinders the Zn-Pt attraction, leading to a non-distorted first layer ZnPc in contact with Pt(111)-I $left(sqrt{3}timessqrt{3}right)$ or Pt(111)-I $left(sqrt{7}timessqrt{7}right)$, and a more homogeneous charge distribution and charge transfer at the interface. On increased ZnPc thickness iodine is dissolved in the organic film where it acts as an electron acceptor dopant.
Interfacial charge transfer is widely assumed to obey Butler-Volmer kinetics. For certain liquid-solid interfaces, Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report a simple method to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures. The fitted reorganization energy matches the Born solvation energy for electron transfer from carbon to the iron redox site. The kinetics are thus limited by electron transfer at the solid-solid (carbon-LixFePO4) interface, rather than by ion transfer at the liquid-solid interface, as previously assumed. The proposed experimental method generalizes Chidseys method for phase-transforming particles and porous electrodes, and the results show the need to incorporate Marcus kinetics in modeling batteries and other electrochemical systems.
We studied by angle-resolved photoelectron spectroscopy the strain-related structural transition from a pseudomorphic monolayer (ML) to a striped incommensurate phase in an Ag thin film grown on Pt(111). We exploited the surfactant properties of Bi to grow ordered Pt(111)-xMLAg-Bi trilayers with 0 < x < 5 ML, and monitored the dispersion of the Bi-derived interface states to probe the structure of the underlying Ag film. We find that their symmetry changes from threefold to sixfold and back to threefold in the Ag coverage range studied. Together with previous scanning tunneling microscopy and photoelectron diffraction data, these results provide a consistent microscopic description of the coverage-dependent structural transition.
We investigate the electronic dynamics of a model organic photovoltaic (OPV) system consisting of polyphenylene vinylene (PPV) oligomers and a [6,6]-phenyl C61-butyric acid methylester (PCBM) blend using a mixed molecular mechanics/quantum mechanics (MM/QM) approach. Using a heuristic model that connects energy gap fluctuations to the average electronic couplings and decoherence times, we provide and estimate of the state-to-state internal conversion rates within the manifold of the lowest few electronic excitations. We show that the electronic dynamics of the OPV are dramatically altered by varying the positions of the molecules simulated at the interface. The lowest few excited states of the model interface rapidly mix allowing low frequency C-C out of plain torsions to modulate the potential energy surface such that the system can sample both intermolecular charge-transfer and charge-separated electronic configurations on sub 100 fs time scales. Our simulations support an emerging picture of carrier generation in OPV systems in which interfacial electronic states can rapidly decay into charge-separated and current producing states via coupling to vibronic degrees of freedom.
The full monolayer of pentacene adsorbed on rutile TiO$_2$(110) provides an intriguing model to study charge-transfer excitations where the optically excited electrons and holes reside on different sides of the internal interface between the pentacene monolayer and the TiO$_2$ surface. In this work we investigate the electronic properties of this system with density functional theory, and compute its excitonic and optical properties making use of emph{ab initio} matrix elements. The pentacene molecules are found to lie flat on the surface, head to tail, and slightly tilted towards the troughs of the oxygen rows of the surface --- in agreement with experiment. Molecular states appear in the band gap of the clean TiO$_2$ surface which enable charge transfer excitations directly from the molecular HOMO to the TiO$_2$ conduction band. The calculated optical spectrum shows a strong polarization dependence and displays excitonic resonances corresponding to the charge-transfer states. We characterize the computed excitons by their symmetry and location in k-space and use this information to explain the polarization dependence of the optical spectrum.
Polarization dependence of resonant anomalous surface x-ray scattering (RASXS) was studied for interfaces buried in electrolytes or in high-pressure gas. We demonstrate that RASXS exhibits strong polarization dependence when the surface is only slightly modified by adsorption of light elements such as carbon monoxide on platinum surfaces. s- and p-polarization RASXS data were simulated with the latest version of ab initio multiple scattering calculations (FEFF8.2). Elementary considerations are additionally presented for the origin of the polarization dependence in RASXS.