Evaluating the Effect of 18O Incorporation on the Vibrational Spectra of Vaterite and Calcite

Calcium carbonates are critical in biomineralization processes and as functional materials. For many applications, isotope enrichment in these materials allows researchers to monitor reaction pathways and retrace environmental signatures. When using vibrational spectroscopy, isotopic composition is currently derived by summing the concentration of each isotopologue, assumed to be directly obtainable from the band intensity, divided by the content of the isotope within the different isotopologues (e.g., C16O3, C16O218O, C16O18O2 and C18O3). However, this approach relies on the assumption that each isotopologue band has an equivalent intensity when present at the same concentration within the crystal structure. Here, using a joint experimental and theoretical approach we test the spectral behavior of the O-isotopologues by examining the effect of a key isotopic tracer, 18O, on the vibrational spectra of the calcium carbonate phases calcite and vaterite. We demonstrate that isotopic substitution changes both band positions and band intensities to different extents, depending on the vibrational spectroscopy method used and the bands examined. For calcite, the υ1 symmetrical stretching Raman-active bands related to individual isotopologues are found to have very similar intensities and are not affected by changes in isotopologue distribution within the material. Fitting these bands resulted in a consistent underestimation of the isotopic enrichment of only 1%, thus they are expected to be useful for estimating 18O-enrichment extent in future experimental work. In contrast, vaterite vibrational bands change more extensively and thus cannot be used directly to determine the 18O concentration within the material. These results are expected to contribute to a deeper und less ambiguous understanding of evaluating isotopic enrichment effects in the vibrational spectra of calcium carbonates

A computational study of the interaction of organic surfactants with goethite alpha-FeO(OH) surfaces

We have studied the adsorption of three organic molecules onto different surfaces of goethite α-FeO(OH) using atomistic simulation techniques. New interatomic potentials for the interaction between goethite and the organic molecules were developed. In the majority of cases the organic molecules were found to be capable of forming a coordinate bond via their carbonyl oxygen atom with a surface iron ion. In addition, weaker hydrogen bonds were formed between the organic molecules and the surfaces. The largest adsorption energies were obtained for the modes of adsorption where the organic molecules bridged or spanned the periodic grooves or dips present on the goethite surfaces, thus forming several interactions between the molecule and the surface. Among all adsorbates studied, the hydroxamic acid molecule in the eclipsed conformation releases the largest adsorption energy when it interacts with goethite surfaces, followed by the staggered conformations of hydroxyethanal and methanoic acid molecules. The adsorption energies are in the range of −60.0 to −186.4 kJ mol−1. Due to the surface structure, as well as the flexibility and size of hydroxamic acid and hydroxyethanal, in most cases these adsorbate molecules lose their planarity with respect to the structure of the isolated molecules. We found that the replacement of pre-adsorbed water by the organic adsorbates is an exothermic process on all the goethite surfaces studied. The removal by sorption onto iron particles of humic and fulvic acids, the major substituents of natural organic matter (NOM) that pollutes aquifers and soils, is corroborated by our calculations of the adsorption of surfactants with the same functional groups as the surfaces of oxidised iron particles

Mind the interface gap: exposing hidden interface defects at the epitaxial heterostructure between CuO and Cu2O

Well designed and optimized epitaxial heterostructures lie at the foundation of materials development for photovoltaic, photocatalytic, and photoelectrochemistry applications. Heterostructure materials offer tunable control over charge separation and transport at the same time preventing recombination of photogenerated excitations at the interface. Thus, it is of paramount importance that a detailed understanding is developed as the basis for further optimization strategies and design. Oxides of copper are nontoxic, low cost, abundant materials with a straightforward and stable manufacturing process. However, in individual applications, they suffer from inefficient charge transport of photogenerated carriers. Hence, in this work, we investigate the role of the interface between epitaxially aligned CuO and Cu2O to explore the potential benefits of such an architecture for more efficient electron and hole transfer. The CuO/Cu2O heterojunction nature, stability, bonding mechanism, interface dipole, electronic structure, and band bending were rationalized using hybrid density functional theory calculations. New electronic states are identified at the interface itself, which are originating neither from lattice mismatch nor strained Cu–O bonds. They form as a result of a change in coordination environment of CuO surface Cu2+ cations and an electron transfer across the interface Cu1+–O bond. The first process creates occupied defect-like electronic states above the valence band, while the second leaves hole states below the conduction band. These are constitutional to the interface and are highly likely to contribute to recombination effects competing with the improved charged separation from the suitable band bending and alignment and thus would limit the expected output photocurrent and photovoltage. Finally, a favorable effect of interstitial oxygen defects has been shown to allow for band gap tunability at the interface but only to the point of the integral geometrical contact limit of the heterostructure itself

Changes in CO2 Adsorption Affinity Related to Ni Doping in FeS Surfaces: A DFT-D3 Study

Metal sulphides constitute cheap, naturally abundant, and environmentally friendly materials for energy storage applications and chemistry. In particular, iron (II) monosulphide (FeS, mackinawite) is a material of relevance in theories of the origin of life and for heterogenous catalytic applications in the conversion of carbon dioxide (CO2) towards small organic molecules. In natural mackinawite, Fe is often substituted by other metals, however, little is known about how such substitutions alter the chemical activity of the material. Herein, the effect of Ni doping on the structural, electronic, and catalytic properties of FeS surfaces is explored via dispersion-corrected density functional theory simulations. Substitutional Ni dopants, introduced on the Fe site, are readily incorporated into the pristine matrix of FeS, in good agreement with experimental measurements. The CO2 molecule was found to undergo deactivation and partial desorption from the doped surfaces, mainly at the Ni site when compared to undoped FeS surfaces. This behaviour is attributed to the energetically lowered d-band centre position of the doped surface, as a consequence of the increased number of paired electrons originating from the Ni dopant. The reaction and activation energies of CO2 dissociation atop the doped surfaces were found to be increased when compared to pristine surfaces, thus helping to further elucidate the role Ni could have played in the reactivity of FeS. It is expected that Ni doping in other Fe-sulphides may have a similar effect, limiting the catalytic activity of these phases when this dopant is present at their surfaces

Simultaneous analysis of multiple classes of antimicrobials in environmental water samples using SPE coupled with UHPLC-ESI-MS/MS and isotope dilution

© 2016 Elsevier B.V. A robust and sensitive analytical method was developed for the simultaneous analysis of 21 target antimicrobials in different environmental water samples. Both single SPE and tandem SPE cartridge systems were investigated to simultaneously extract multiple classes of antimicrobials. Experimental results showed that good extraction efficiencies (84.5-105.6%) were observed for the vast majority of the target analytes when extraction was performed using the tandem SPE cartridge (SB+HR-X) system under an extraction pH of 3.0. HPLC-MS/MS parameters were optimized for simultaneous analysis of all the target analytes in a single injection. Quantification of target antimicrobials in water samples was accomplished using 15 isotopically labeled internal standards (ILISs), which allowed the efficient compensation of the losses of target analytes during sample preparation and correction of matrix effects during UHPLC-MS/MS as well as instrument fluctuations in MS/MS signal intensity. Method quantification limit (MQL) for most target analytes based on SPE was below 5 ng/L for surface waters, 10 ng/L for treated wastewater effluents, and 15 ng/L for raw wastewater. The method was successfully applied to detect and quantify the occurrence of the target analytes in raw influent, treated effluent and surface water samples

On-demand semiconductor single-photon source with near-unity indistinguishability

Single photon sources based on semiconductor quantum dots offer distinct advantages for quantum information, including a scalable solid-state platform, ultrabrightness, and interconnectivity with matter qubits. A key prerequisite for their use in optical quantum computing and solid-state networks is a high level of efficiency and indistinguishability. Pulsed resonance fluorescence (RF) has been anticipated as the optimum condition for the deterministic generation of high-quality photons with vanishing effects of dephasing. Here, we generate pulsed RF single photons on demand from a single, microcavity-embedded quantum dot under s-shell excitation with 3-ps laser pulses. The pi-pulse excited RF photons have less than 0.3% background contributions and a vanishing two-photon emission probability. Non-postselective Hong-Ou-Mandel interference between two successively emitted photons is observed with a visibility of 0.97(2), comparable to trapped atoms and ions. Two single photons are further used to implement a high-fidelity quantum controlled-NOT gate.Comment: 11 pages, 11 figure

Ultrafast optical control of entanglement between two quantum dot spins

The interaction between two quantum bits enables entanglement, the two-particle correlations that are at the heart of quantum information science. In semiconductor quantum dots much work has focused on demonstrating single spin qubit control using optical techniques. However, optical control of entanglement of two spin qubits remains a major challenge for scaling from a single qubit to a full-fledged quantum information platform. Here, we combine advances in vertically-stacked quantum dots with ultrafast laser techniques to achieve optical control of the entangled state of two electron spins. Each electron is in a separate InAs quantum dot, and the spins interact through tunneling, where the tunneling rate determines how rapidly entangling operations can be performed. The two-qubit gate speeds achieved here are over an order of magnitude faster than in other systems. These results demonstrate the viability and advantages of optically controlled quantum dot spins for multi-qubit systems.Comment: 24 pages, 5 figure