Observing the intricate chemical transformation of an individual molecule as it undergoes a complex reaction is a long-standing challenge in molecular imaging. Advances in scanning probe microscopy now provide the tools to visualize not only the frontier orbitals of chemical reaction partners and products, but their internal covalent bond configurations as well. We used noncontact atomic force microscopy to investigate reaction-induced changes in the detailed internal bond structure of individual oligo-(phenylene-1,2-ethynylenes) on a (100) oriented silver surface as they underwent a series of cyclization processes. Our images reveal the complex surface reaction mechanisms underlying thermally induced cyclization cascades of enediynes. Calculations using ab initio density functional theory provide additional support for the proposed reaction pathways.

Using density functional theory calculations, we study trends in the CO oxidation activity for different metals and surfaces. Specifically, we show how the activity of (111) close-packed surfaces, (211) stepped surfaces, (532) kinked surfaces, 55 atom cuboctahedral clusters, and 12 atom cluster models changes with the coordination number of atoms at the active sites. This effect is shown to be electronic in nature, as low coordinated metal atoms, which bind reactants most strongly, have the highest energy metal d states.

Photocatalytic and photovoltaic activity depends on the optimal alignment of electronic levels at the molecule/semiconductor interface. Establishing level alignment experimentally is complicated by the uncertain chemical identity of the surface species. We address the assignment of the occupied and empty electronic levels for the prototypical photocatalytic system of methanol on a rutile TiO 2 (110) surface. Using many-body quasiparticle (QP) techniques we show that the frontier levels measured in ultraviolet photoelectron and two photon photoemission spectroscopy experiments can be assigned with confidence to the molecularly chemisorbed methanol, rather than its decomposition product, the methoxy species. We find the highest occupied molecular orbital (HOMO) of the methoxy species is much closer to the valence band maximum, suggesting why it is more photocatalytically active than the methanol molecule. We develop a general semi-quantitative model for predicting manybody QP energies based on the appropriate description of electronic screening within the bulk, molecular or vacuum regions of the wavefunctions at molecule/semiconductor interfaces. M olecular energy levels are strongly renormalized when molecules are brought into contact with surfaces. 1 The energy positions of the frontier highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of the adsorbate with respect to the valence band maximum and conduction band minimum (VBM and CBM) of photocatalytic substrates define the potentials for electron transfer across a molecule/semiconductor interface. Photoelectron spectroscopy can accurately determine the alignment of the frontier orbitals of the adsorbate with respect to the substrate bands provided that the chemical state of the chemisorbed molecule is known. The chemical assignment and correct description of the molecule-photocatalyst interaction require theory to accurately predict the electronic structure of the coupled system.We consider the electronic structure of methanol chemisorbed intact or in its partially dissociated methoxy form on the stoichiometric rutile TiO 2 (110) surface. Methanol is well established as a sacrificial hole scavenger in the photocatalytic splitting of H 2 O by UV light excitation of TiO 2 nanocolloids. 2,3 Experimentally, the electronic structure and photocatalytic activity of methanol on the single crystal rutile TiO 2 (110) surface under ultra-high vacuum (UHV) conditions has been investigated by ultraviolet, X-ray, and two photon photoelectron spectroscopy (UPS, XPS, and 2PP), 4-7 scanning tunnelling microscopy 7-9 (STM), and mass spectrometric analysis of reaction products. 10,11 These experiments have reached contradictory conclusions regarding whether the empty "wet electron" level 12 that is observed in 2PP spectra of methanol covered TiO 2 surfaces should be assigned to the methanol or methoxy species. 6,7 Furthermore, although it is clear that the methoxy species is more photocatalytically active than the methanol molecule, there is stil...

The observation of a many-body, Fermi-energy edge singularity in the low-temperature photoluminescence spectra of InGaAs-InP quantum wells is reported. Strong enhancement of the photoluminescence intensity towards the electron Fermi energy {E%) is observed, due to multiple electron-hole scattering processes to states above E%. Recombination of electrons in states up to E% is allowed by hole localization. The many-body processes are analogous to the core-hole phenomena in the soft-x-ray emission spectra of metals.

Electronic level alignment at the interface between an adsorbed molecular layer and a semiconducting substrate determines the activity and efficiency of many photocatalytic materials. Standard density functional theory (DFT)-based methods have proven unable to provide a quantitative description of this level alignment. This requires a proper treatment of the anisotropic screening, necessitating the use of quasiparticle (QP) techniques. However, the computational complexity of QP algorithms has meant a quantitative description of interfacial levels has remained elusive. We provide a systematic study of a prototypical interface, bare and methanol-covered rutile TiO2(110) surfaces, to determine the type of many-body theory required to obtain an accurate description of the level alignment. This is accomplished via a direct comparison with metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), and two-photon photoemission (2PP) spectroscopy. We consider GGA DFT, hybrid DFT, and G0W0, scQPGW1, scQPGW0, and scQPGW QP calculations. Our results demonstrate that G0W0, or our recently introduced scQPGW1 approach, are required to obtain the correct alignment of both the highest occupied and lowest unoccupied interfacial molecular levels (HOMO/LUMO). These calculations set a new standard in the interpretation of electronic structure probe experiments of complex organic molecule/semiconductor interfaces.

Using density functional theory (DFT), we analyze the influence of five classes of functional groups, as exemplified by NO(2), OCH(3), CH(3), CCl(3), and I, on the transport properties of a 1,4-benzenedithiolate (BDT) and 1,4-benzenediamine (BDA) molecular junction with gold electrodes. Our analysis demonstrates how ideas from functional group chemistry may be used to engineer a molecule's transport properties, as was shown experimentally and using a semiempirical model for BDA [Nano Lett. 7, 502 (2007)]. In particular, we show that the qualitative change in conductance due to a given functional group can be predicted from its known electronic effect (whether it is sigma/pi donating/withdrawing). However, the influence of functional groups on a molecule's conductance is very weak, as was also found in the BDA experiments. The calculated DFT conductances for the BDA species are five times larger than the experimental values, but good agreement is obtained after correcting for self-interaction and image charge effects.

We address one of the main challenges to TiO2-photocatalysis, namely band gap narrowing, by combining nanostructural changes with doping. With this aim we compare TiO2's electronic properties for small 0D clusters, 1D nanorods and nanotubes, 2D layers, and 3D surface and bulk phases using different approximations within density functional theory and GW calculations. In particular, we propose very small (R 5Å) but surprisingly stable nanotubes with promising properties. The nanotubes are initially formed from TiO2 layers with the PtO2 structure, with the smallest (2,2) nanotube relaxing to a rutile nanorod structure. We find that quantum confinement effects -as expected -generally lead to a widening of the energy gap. However, substitutional doping with boron or nitrogen is found to give rise to (meta-)stable structures and the introduction of dopant and mid-gap states which effectively reduce the band gap. Boron is seen to always give rise to n-type doping while depending on the local bonding geometry, nitrogen may give rise to n-type or p-type doping. For undercoordinated TiO2 surface structures found in clusters, nanorods, nanotubes, layers and surfaces nitrogen gives rise to acceptor states while for larger clusters and bulk structures donor states are introduced.

The molecule/metal interface is the key element in charge injection devices. It can be generally defined by a monolayer-thick blend of donor and/or acceptor molecules in contact with a metal surface. Energy barriers for electron and hole injection are determined by the offset from HOMO (highest occupied) and LUMO (lowest unoccupied) molecular levels of this contact layer with respect to the Fermi level of the metal electrode. However, the HOMO and LUMO alignment is not easy to elucidate in complex multicomponent, molecule/metal systems. We demonstrate that core-level photoemission from donor-acceptor/metal interfaces can be used to straightforwardly and transparently assess molecular-level alignment. Systematic experiments in a variety of systems show characteristic binding energy shifts in core levels as a function of molecular donor/acceptor ratio, irrespective of the molecule or the metal. Such shifts reveal how the level alignment at the molecule/metal interface varies as a function of the donor-acceptor stoichiometry in the contact blend.