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The transfer and upgrade of the SPECIES beamline and its endstation to the 1.5 GeV storage ring at the MAX IV Laboratory is reported., The SPECIES beamline has been transferred to the new 1.5 GeV storage ring at the MAX IV Laboratory. Several improvements have been made to the beamline and its endstations during the transfer. Together the Ambient Pressure X-ray Photoelectron Spectroscopy and Resonant Inelastic X-ray Scattering endstations are capable of conducting photoelectron spectroscopy in elevated pressure regimes with enhanced time-resolution and flux and X-ray scattering experiments with improved resolution and flux. Both endstations offer a unique capability for experiments at low photon energies in the vacuum ultraviolet and soft X-ray range. In this paper, the upgrades on the endstations and current performance of the beamline are reported.

We present the first experimental study of the frontier orbitals in an ultrathin film of the novel hexa-carbene photosensitizer [Fe(btz)3]3+, where btz is 3,3′-dimethyl-1,1′-bis(p-tolyl)-4,4′-bis(1,2,3-triazol-5-ylidene). Resonant photoelectron spectroscopy (RPES) was used to probe the electronic structure of films where the molecular and oxidative integrities had been confirmed with optical and X-ray spectroscopies. In combination with density functional theory calculations, RPES measurements provided direct and site-selective information about localization and interactions of occupied and unoccupied molecular orbitals. Fe 2p, N 1s, and C 1s measurements selectively probed the metal, carbene, and side-group contributions revealing strong metal–ligand orbital mixing of the frontier orbitals. This helps explain the remarkable photophysical properties of iron-carbenes in terms of unconventional electronic structure properties and favorable metal–ligand bonding interactions—important for the continued development of these type of complexes toward light-harvesting and light-emitting applications.

© 2018 Elsevier Inc. Using a multi-technical approach, we studied the oxidation of anatase TiO 2 (1 0 1)-supported vanadium (V) clusters at room temperature. We found by ex situ XPS that the highest oxidation state is +4 at sub-monolayer coverage regardless of the O 2 pressure, and STM studies revealed that the initial oxidation proceeds through oxygen-induced disintegration of V clusters into monomeric VO 2 species. By contrast, for ∼2 monolayer V coverage, a partial oxidation to V 5+ is achieved. By in situ APXPS measurements, we found that V can be maintained in the V 5+ oxidation state irrespective of the coverage; however, in the sub-monolayer range, an O 2 pressure of at least ∼1 × 10 −5 mbar is needed. Our results suggest an enhanced reducibility of V in direct contact with the TiO 2 support compared to V in the 2nd layer, which is in line with the observed optimum V 2 O 5 loading in catalytic applications just slightly below a full monolayer. (Less)

The electronic structure and excited state properties of a series of iron carbene photosensitizers are elucidated through a combination of X-ray absorption measurements and density functional theory calculations. The X-ray absorption spectra are discussed with regard to the unusual bonding environment in these carbene complexes, highlighting the difference between ferrous and ferric carbene complexes. The valence electronic structure of the core excited Fe III - 3 d 5 complex is predicted by calculating the properties of a Co III - 3 d 6 carbene complex using the Z+1 approximation. Insight is gained into the potential of sigma-donating ligands as strategy to tune properties for light harvesting applications.

Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3'-dimethyl-1,1'-bis(p-tolyl)-4,4'-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(iii) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

The atomic contributions to valence electronic structure for 37 ionic liquids (ILs) are identified using a combination of variable photon energy XPS, resonant Auger electron spectroscopy (RAES) and a subtraction method. The ILs studied include a diverse range of cationic and anionic structural moieties. We introduce a new parameter for ILs, the energy difference between the energies of the cationic and anionic highest occupied fragment orbitals (HOFOs), which we use to identify the highest occupied molecular orbital (HOMO). The anion gave rise to the HOMO for 25 of the 37 ILs studied here. For 10 of the ILs, the energies of the cationic and anionic HOFOs were the same (within experimental error); therefore, it could not be determined whether the HOMO was from the cation or the anion. For two of the ILs, the HOMO was from the cation and not from the anion; consequently it is energetically more favourable to remove an electron from the cation than the anion for these two ILs. In addition, we used a combination of area normalisation and subtraction of XP spectra to produce what are effectively XP spectra for individual ions; this was achieved for seven cations and 14 anions.

Monolayers of C60 and the functionalised fullerene phenyl-C61-butyric acid methyl ester (PCBM) have been prepared on Au(1 1 1) by in situ electrospray deposition. The observation of super-spectator/super-Auger decay in resonant photoemission spectroscopy (RPES) of C60 confirms monolayers prepared using electrospray undergo ultra-fast charge transfer as per previous studies of C60 monolayers on Au(1 1 1) prepared by sublimation. For PCBM, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) show the lowest unoccupied molecular orbital (LUMO) of the molecule overlaps the Fermi-level of the metal surface. Despite this, no evidence of ultra-fast charge transfer is observed in the RPES of PCBM.

Using a radio-frequency ion trap to study ion-molecule reactions under isolated conditions, we report a direct experimental determination of reaction rate constants for the sequential oxidation of iodine anions by ozone at room temperature (300 K). The results are R1: I- + O3 → IO- + O2, k1 = (7 ± 2) × 10-12 cm3 s-1; R2: IO- + O3 → IO2- + O2, k2 = (10 ± 2) × 10-9 cm3 s-1; R3: IO2- + O3 → IO3- + O2, k3 = (16 ± 2) × 10-9 cm3 s-1. More oxidized forms such as IO4- and IO5- were not observed. Additionally, we performed quantum chemical calculations to elucidate the energetics of these oxidation reactions.

Two-dimensional resonant inelastic x-ray scattering (RIXS) and resonant photoelectron spectroscopy (RPES) maps are presented for multilayer and monolayer coverages of an aromatic molecule (bi-isonicotinic acid) on the rutile TiO

The surface-assisted synthesis of gold-organometallic hybrids on the Au(111) surface both by thermo- and light-initiated dehalogenation of bromo-substituted tetracene is reported. Combined X-ray photoemission (XPS) and scanning tunneling microscopy (STM) data reveal a significant increase of the surface order when mild reaction conditions are combined with 405 nm light irradiation.

The adsorption and charge transfer dynamics of the organic molecule bi-isonicotinic acid (4,4?-dicarboxy-2,2?-bipyridine) on single crystal Ag(111) has been studied using synchrotron radiation-based photoemission, x-ray absorption and resonant core spectroscopies. Measurements for multilayer and monolayer coverage are used to determine the nature of the molecule-surface interactions and the molecular orientation. An experimental density of states for the monolayer with respect to the underlying metal surface is obtained by combining x-ray absorption spectroscopy at the N 1s edge and valence photoemission to measure the unoccupied and occupied valence states, respectively. This shows that the lowest unoccupied molecular orbital in the core-excited state lies energetically below the Fermi level of the surface allowing charge transfer from the metal into this orbital. Resonant photoelectron spectroscopy was used to probe this charge transfer in the context of super-spectator and super-Auger electron transitions. The results presented provide a novel interpretation of resonant core-level spectroscopy to explore ultra-fast charge transfer between an adsorbed organic molecule and a metal surface through the observation of electrons from the metal surface playing a direct role in the core-hole decay of the core-excited molecule.

Achieving control of the surface chemistry of colloidal quantum dots (CQDs) is essential to fully exploit their properties in solar cells, but direct measurement of the chemistry and electronic structure in the outermost atomic layers is challenging. Here we probe the surface oxidation and passivation of cation-exchanged PbS/CdS core/shell CQDs with sub nm-scale precision using synchrotron-radiation-excited depth-profiling photoemission. We investigate the surface composition of the topmost 1-2.5 nm of the CQDs as a function of depth, for CQDs of varying CdS shell thickness, and examine how the surface changes after prolonged air exposure. We demonstrate that the Cd is localized at the surface of the CQDs. The surface-localized products of oxidation are identified, and the extent of oxidation quantified. We show that oxidised sulfur species are progressively eliminated as Cd replaces Pb at the surface. A sub-monolayer surface 'decoration' of Cd is found to be effective in passivating the CQDs. We show that the measured energy-level alignments at PbS/CdS colloidal quantum dot surfaces differ from those expected on the basis of bulk band offsets, and are strongly affected by the oxidation products. We develop a model for the passivating action of Cd. The optimum shell thickness (of around 0.1 nm, previously found to give maximised power conversion efficiency in PbS/CdS solar cells) is found to correspond to a trade-off between the rate of oxidation and the introduction of a surface barrier to charge transport.

Charge transfer interactions between C60 and the metal surfaces of Ag(111), Cu(111), Au(111) and Pt(111) have been studied using synchrotron-based photoemission, resonant photoemission and X-ray absorption spectroscopies. By placing the X-ray absorption and valence band spectra on a common binding energy scale, the energetic overlap of the unoccupied molecular orbitals with the density of states of the underlying metal surface have been assessed in the context of possible charge transfer pathways. Resonant photoemission and resonant Auger data, measuring the valence region as a function of photon energy for C60 adsorbed on Au(111) reveals three constant high kinetic energy features associated with Auger-like core-hole decay involving an electron transferred from the surface to the LUMO of the molecule and electrons from the three highest occupied molecular orbitals, respectively and in the presence of ultra-fast charge transfer of the originally photoexcited molecule to the surface. Data for the C60/Ag(111) surface reveals an additional Auger-like feature arising from a core-hole decay process involving more than one electron transferred from the surface into the LUMO. An analysis of the relative abundance of these core-hole decay channels estimates that on average 2.4 $\pm$ 0.3 electrons are transferred from the Ag(111) surface into the LUMO. A core-hole clock analysis has also been applied to assess the charge transfer coupling in the other direction, from the molecule to the Au(111) and Ag(111) surfaces. Resonant photoemission and resonant Auger data for C60 molecules adsorbed on the Pt(111) and Cu(111) surfaces are shown to exhibit no super-Auger features, which is attributed to the strong modification of the unoccupied molecular orbitals arising from stronger chemical coupling of the molecule to the surface.

N 1s Resonant Inelastic X-ray Scattering (RIXS) was used to probe the molecular electronic structure of the ruthenium photosensitizer complex cis-bis(isothiocyanato) bis(2,2'-bipyridyl-4,4'-dicarboxylato) ruthenium(II), known as "N3." In order to interpret these data, crystalline powder samples of the bipyridine-dicarboxylic acid ligand ("bi-isonicotinic acid") and the single ring analog "isonicotinic acid" were studied separately using the same method. Clear evidence for intermolecular hydrogen bonding is observed for each of these crystalline powders, along with clear vibronic coupling features. For bi-isonicotinic acid, these results are compared to those of a physisorbed multilayer, where no hydrogen bonding is observed. The RIXS of the "N3" dye, again prepared as a bulk powder sample, is interpreted in terms of the orbital contributions of the bi-isonicotinic acid and thiocyanate ligands by considering the two different nitrogen species. This allows direct comparison with the isolated ligand molecules where we highlight the impact of the central Ru atom on the electronic structure of the ligand. Further interpretation is provided through complementary resonant photoemission spectroscopy and density functional theory calculations. This combination of techniques allows us to confirm the localization and relative coupling of the frontier orbitals and associated vibrational losses.

The adsorption of two ruthenium-based dye complexes containing dipyrrin-based ligands has been studied on the rutile TiO2(110) surface using synchrotron-based electron spectroscopy. The dye complexes studied were bis(5-(4-carboxyphenyl)-4,6-dipyrrin)bis(dimethyl sulfoxide)ruthenium(II) and bis(5-(4-carboxyphenyl)-4,6-dipyrrin)(2,2′-bipyridine)ruthenium(II). The dye molecules were deposited using in situ electrospray deposition, which allows for the deposition of thermally fragile molecules in ultrahigh vacuum. Photoemission studies were used to provide experimental data on the bonding geometry of the dye complexes to the rutile TiO2(110) substrate and to provide data on molecular orbitals involved in the charge transfer process. DFT calculations of the molecules adsorbed onto the rutile TiO2(110) surface have also been performed to identify the most energetically favorable bonding geometry.

Two-dimensional resonant inelastic x-ray scattering (RIXS) and resonant photoelectron spectroscopy (RPES) maps are presented for multilayer and monolayer coverages of an aromatic molecule (biisonicotinic acid) on the rutile TiO2(110) single crystal surface. The data reveal ultra-fast intramolecular vibronic coupling upon core excitation from the N 1s orbital into the lowest unoccupied molecular orbital (LUMO) derived resonance. In the RIXS measurements, this results in the splitting of the participator decay channel into a purely elastic line which disperses linearly with excitation energy and a vibronic coupling channel at constant emission energy. In the RPES measurements, the vibronic coupling results in a linear shift in binding energy of the participator channel as the excitation is tuned over the LUMO-derived resonance. Localisation of the vibrations on the molecule on the femtosecond time scale results in predominantly inelastic scattering from the core-excited state in both the physisorbed multilayer and the chemisorbed monolayer. Published by AIP Publishing.

We present for the first time two-dimensional resonant inelastic x-ray scattering (RIXS) maps of multilayer and monolayer bi-isonicotinic acid adsorbed on the rutile TiO2(110) single crystal surface. This enables the elastic channel to be followed over the lowest unoccupied molecular orbitals resonantly excited at the N 1s absorption edge. The data also reveal ultra-fast intramolecular vibronic coupling, particularly during excitation into the lowest unoccupied molecular orbital-derived resonance. Both elastic scattering and the vibronic coupling loss features are expected to contain the channel in which the originally excited electron is directly involved in the core-hole decay process. This allows RIXS data for a molecule coupled to a wide bandgap semiconductor to be considered in the same way as the core-hole clock implementation of resonant photoemission spectroscopy (RPES). However, contrary to RPES measurements, we find no evidence for the depletion of the participator channel under the conditions of ultra-fast charge transfer from the molecule to the substrate densities of states, on the time scale of the core-hole lifetime. These results suggest that the radiative core-hole decay processes in RIXS are not significantly modified by charge transfer on the femtosecond time scale in this system.

The interaction of the dye molecule N3 (cis-bis(isothiocyanato)bis(2,2-bipyridyl-4,4'-dicarboxylato)-ruthenium(II)) with the ultra-thin oxide layer on a AlNi(110) substrate, has been studied using synchrotron radiation based photoelectron spectroscopy, resonant photoemission spectroscopy (RPES) and near edge X-ray absorption fine structure spectroscopy (NEXAFS). Calibrated X-ray absorption and valence band spectra of the monolayer and multilayer coverages reveal that charge transfer is possible from the molecule to the AlNi(110) substrate via tunnelling through the ultra-thin oxide layer and into the conduction band edge of the substrate. This charge transfer mechanism is possible from the LUMO+2&3 in the excited state but not from the LUMO, therefore enabling core-hole clock analysis, which gives an upper limit of $6.0\pm$2.5fs for the transfer time. This indicates that ultra-thin oxide layers are a viable material for use in dye-sensitized solar cells (DSSC), which may lead to reduced recombination effects and improved efficiencies of future devices.

The self-assembly of organic molecules on surfaces is a promising approach for the development of nanoelectronic devices. Although a variety of strategies have been used to establish stable links between molecules, little is known about the electrical conductance of these links. Extended electronic states, a prerequisite for good conductance, have been observed for molecules adsorbed on metal surfaces. However, direct conductance measurements through a single layer of molecules are only possible if the molecules are adsorbed on a poorly conducting substrate. Here we use a nanoscale four-point probe to measure the conductivity of a self-assembled layer of cobalt phthalocyanine on a silver-terminated silicon surface as a function of thickness. For low thicknesses, the cobalt phthalocyanine molecules lie flat on the substrate, and their main effect is to reduce the conductivity of the substrate. At higher thicknesses, the cobalt phthalocyanine molecules stand up to form stacks and begin to conduct. These results connect the electronic structure and orientation of molecular monolayer and few-layer systems to their transport properties, and should aid in the rational design of future devices.

The room temperature conductance of Bi(111) was measured using microscopic four point probes with a contact spacing down to 500 nm. The conductance is remarkably similar to that of the bulk, indicating that surface scattering is not a major mechanism for restricting the mobility at this length scale. Also, the high density of electronic surface states on Bi(111) does not appear to have a major influence on the measured conductance. The lower limit for the resistivity due to electronic surface states is found to be around 5 Omega. With such a value for the surface resistivity, surface conduction should not be a significant factor to inhibit the observation of the predicted semiconductor to semimetal transition for thin films of Bi. ©2008 American Institute of Physics

Two single molecule magnets based on the dodecamanganese (III, IV) cluster with either benzoate or terphenyl-4-carboxylate ligands, have been studied on the Au(111) and rutile TiO2(110) surfaces. We have used in situ electrospray deposition to produce a series of surface coverages from a fraction of a monolayer to multilayer films in both cases. X-ray absorption spectroscopy measured at the Mn L-edge (Mn 2p) has been used to study the effect of adsorption on the oxidation states of the manganese atoms in the core. In the case of the benzoate-functionalised complex reduction of the manganese metal centres is observed due to the interaction of the manganese core with the underlying surface. In the case of terphenyl-4-carboxylate, the presence of this much larger ligand prevents the magnetic core from interacting with either the gold or the titanium dioxide surfaces and the characteristic Mn(3+) and Mn(4+) oxidation states necessary for magnetic behaviour are preserved.

Charge transfer from photoexcited dye molecules to a semiconductor substrate forms the basis of dye sensitized solar cells (DSCs); the overall effectiveness of a DSC device is critically dependent upon the efficiency of this process due to competition with other de-excitation channels. In this paper, we experimentally derive timescales for the charge transfer process in model water splitting DSCs. We studied two organometallic dye complexes adsorbed onto a rutile TiO(2)(110) substrate, the dye molecules were deposited in ultra-high vacuum using electrospray deposition. DFT simulations were used to calculate the spatial distribution of orbitals relevant to the charge transfer process. The core-hole clock implementation of resonant photoemission spectroscopy was used to determine upper limits on charge transfer timescales for previously unoccupied orbitals, which were found to be in the low-femtosecond regime apart from one orbital found to have an upper limit in the sub-femtosecond regime.

We present a complementary metal-oxide-semiconductor compatible, nanoscale 12-point-probe based on TiW electrodes placed on a SiO2 monocantilever. Probes are mass fabricated on Si wafers by a combination of electron beam and UV lithography, realizing TiW electrode tips with a width down to 250 nm and a probe pitch of 500 nm. In-air four-point measurements have been performed on indium tin oxide, ruthenium, and titanium-tungsten, showing good agreement with values obtained by other four-point probes. In-vacuum four-point resistance measurements have been performed on clean Bi(111) using different probe spacings. The results show the expected behavior for bulk Bi, indicating that the contribution of electronic surface states to the transport properties is very small. (C) 2008 American Institute of Physics.

Biomimetic sulfur-deficient indium sulfide (In2.77S4) was synthesized by a template-assisted hydrothermal method using leaves of Mimosa pudica as a template for the first time. The effect of this template in modifying the morphology of the semiconductor particles was determined by physicochemical characterization, revealing an increase in surface area, decrease in microsphere size and pore size and an increase in pore volume density in samples synthesized with the template. X-ray photoelectron spectroscopy (XPS) analysis showed the presence of organic sulfur (S O/S C/S H) and sulfur oxide species ( SO2, SO32−, SO42−) at the surface of the indium sulfide in samples synthesized with the template. Biomimetic indium sulfide also showed significant amounts of Fe introduced as a contaminant present on the Mimosa pudica leaves. The presence of these sulfur and iron species favors the photocatalytic activity for hydrogen production by their acting as a sacrificial reagent and promoting water oxidation on the surface of the templated particles, respectively. The photocatalytic hydrogen production rates over optimally-prepared biomimetic indium sulfide and indium sulfide synthesized without the organic template were 73 and 22 μmol g−1, respectively, indicating an improvement by a factor of three in the templated sample.