Synchrotron PEEM and ToF‐SIMS study of oxidized heterogeneous pentlandite,pyrrhotite and chalcopyrite

Synchrotron‐based photoemission electron microscopy (PEEM; probing the surface region) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS; probing the uppermost surface layer) have been used to image naturally heterogeneous samples containing chalcopyrite (CuFeS₂), pentlandite [(Ni,Fe)₉S₈] and monoclinic pyrrhotite (Fe₇S₈) both freshly polished and exposed to pH 9 KOH for 30 min. PEEM images constructed from the metal L₃ absorption edges were acquired for the freshly prepared and solution‐exposed mineral samples. These images were also used to produce near‐edge X‐ray absorption fine‐structure spectra from regions of the images, allowing the chemistry of the surface of each mineral to be interrogated, and the effect of solution exposure on the mineral surface chemistry to be determined. The PEEM results indicate that the iron in the monoclinic pyrrhotite oxidized preferentially and extensively, while the iron in the chalcopyrite and pentlandite underwent only mild oxidation. The ToF‐SIMS data gave a clearer picture of the changes happening in the uppermost surface layer, with oxidation products being observed on all three minerals, and significant polysulfide formation and copper activation being detected for pyrrhotite.     

A comparative X-ray absorption near-edge structure study of bornite,Cu5FeS4, and chalcopyrite,CuFeS2

High resolution Fe L-, Cu L-, S L-edge and O K-edge X-ray absorption near-edge structure (XANES) spectra of synthetic bornite and the samples oxidized in air and leached in a ferric chloride solution have been recorded and compared with the spectra of chalcopyrite. The pre-edge shoulder in the Cu L-edge spectrum of bornite and the strong leading peak in the spectrum of chalcopyrite were attributed to the electron transitions to the minor density of unoccupied Cu 3d states, and the post-edge features were related to the states of s- and p-type. The Fe L-edge XANES showed the presence of predominant Fe²⁺ for chalcopyrite, and some quantity of Fe²⁺ for bornite cannot be excluded despite XPS and Mössbauer spectroscopy had previously detected only Cu⁺ and Fe³⁺ species in both minerals. The Cu L- and S L-edge spectra of bornite considerably modify and become similar to those of chalcopyrite after the oxidative leaching that produces the heavily metal-depleted surface layers, and the Fe L-edge XANES shows only a slightly increased contribution of Fe²⁺. The multiparticle configurations involving Fe²⁺ and Cu²⁺ or holes at S atoms may play a role in the L-spectra.     

Manganese speciation in Diplodon chilensis patagonicus shells: a XANES study

X‐ray absorption near‐edge spectroscopy (XANES) at the Mn K‐edge was used to investigate the environment of Mn in situ within the growth increments of the long‐lived freshwater bivalve species Diplodon chilensis patagonicus. Single XANES spectra and Mn Kα fluorescence distributions were acquired at submillimetre resolution (up to 100 µm × 50 µm), at Mn concentrations below the weight percent range (100–1000 µg g^?1) in a high Ca matrix. The position and intensity of the pre‐edge feature in the shell spectrum resembles best that of the Mn(II)‐bearing reference compounds, suggesting that this is the oxidation state of Mn in the bivalve shells. By comparison with the XANES spectra of selected standard compounds, hypotheses about Mn speciation in the shell are also reported. In particular, different factors, such as provenance, ontogenetic age, variable Mn‐concentrations or seasonal shell deposition seem not to influence the speciation of the metal in this bivalve species.     

Surface chemistry: from vibrational spectroscopy to photoemission spectromicroscopy

Vibrational spectroscopy and core-level photoelectron spectroscopy are two of the most powerful tools for surface chemical analysis. We have used both techniques in conjunction with others to study hydrocarbon radical interactions with metal and semiconductor surfaces as well as thin film deposition processes. These include the investigations of CH₂ and CH₃ reactions on Cu by high resolution electron energy loss spectroscopy (HREELS), and GaN formation from Ga(CH₃)₃ and NH₃ on SiC by SR-PES. The vibrational analysis has revealed rich surface chemistry of the radicals while the photoemission study has led us to develop new approach for probing ultrafine structures. The effort involves the construction of a scanning photoemission spectromicroscope (SPEM) coupled to a synchrotron radiation light source. Recent results are presented in this brief report.     

Validation of fuzzy logic method for automated mass spectral classification for mineral imaging

Imaging mass spectrometry requires the acquisition and interpretation of hundreds to thousands of individual spectra in order to map the mineral phases within heterogeneous geomatrices. A fuzzy logic inference engine (FLIE) was developed to automate data interpretation. To evaluate the strengths and limitations of FLIE, the chemical images obtained using FLIE were compared with those developed using two chemometric methods: principle component analysis (PCA) and cluster analysis (K-Means). Two heterogeneous geomatrices, a low-grade chalcopyrite ore and basalt, were imaged using a laser-desorption Fourier transform mass spectrometer. Similar mineral distribution patterns in the chalcopyrite ore sample were obtained by the three data analysis methods with most of the differences occurring at the interfaces between mineral phases. PCA missed one minor mineral phase in the chalcopyrite ore sample and did not clearly differentiate among the mineral classes of the basalt. K-Means cluster analysis differentiated among the various mineral phases in both samples, but improperly grouped some spectra in the chalcopyrite sample that only contained unanticipated high mass peaks. Unlike the chemometric methods, FLIE was able to classify spectra as unknowns for those spectra that fell below the confidence level threshold. A nearest neighbor approach, included in FLIE, was used to classify the unknowns to form a visually complete image; however, the unknowns identified by FLIE can be informative because they highlight potential problems or overlooked results. In conclusion, this study validated the fuzzy logic-based approach used in our laboratory and reveald some limitations in the three techniques that were evaluated.     

Single particle tunneling and photoemission spectra in anisotropic layered high-temperature superconductors

We explore the effects of an anisotropic order parameter on the single particle tunneling conductance and on angular integrated and angular resolved photoemission spectra. Adopting a tight-binding model band structure, extendeds-wave pairing and the BCS strategy, we calculate the tunneling conductance for specular and diffuse transmission and the coherent part of the photoemission spectrum. Recent evidence for gap anisotropy, resulting from tunneling perpendicular and parallel to the layers, is traced back tox,y-anisotropy mediated by nearestneighbor intralayer pairing. This anisotropy is also found to be consistent with angular integrated photoemission measurements. It is shown that angular resolved photoemission experiments with high resolution would allow a more detailed identification of this anisotropic superconducting state.     

Covalency in the electronic structure of Fe3O4: An ultraviolet inverse photoemission investigation

The unoccupied electronic structure of an opend-shell transition metal oxide, namely Fe₃O₄, has been addressed by measuring ultraviolet angle-integrated inverse photoemission (IP) spectra acquired in the isochromat mode (hv=10.2-24 eV). Exploitation of photon energy dependence of symmetry-projected IP cross-sections and comparison with the O 1s X-ray absorption spectrum allow us to recognize a strong covalent admixture of Fe [3d; 4 (sp)]-and O (2p)-derived states in this compound.     

Surface states and accumulation nanolayer induced by Ba and Cs adsorption on the n-GaN(0 0 0 1) surface

The Ba and Cs adsorption on the n-GaN(0 0 0 1) surface has been studied in situ by the threshold photoemission spectroscopy using s- and p-polarized light excitation. Two surface bands induced by Ba (Cs) adsorption are revealed in surface photoemission spectra below the Fermi level. The surface-Fermi level position is found to be changed from significantly below the conduction band minimum (CBM) at clean n-GaN surface to high above the CBM at Ba, Cs/n-GaN interfaces, with the transition from depletion to electron accumulation occurring at low coverages. Photoemission from the accumulation nanolayer is found to excite by visible light in the transparency region of GaN. Appearance of an oscillation structure in threshold photoemission spectra of the Ba, Cs/n-GaN interfaces with existing the accumulation layer is found to originate from Fabry–Perot interference in the transparency region of GaN.     

Photoemission studies of ultrathin Cs,Ba/InN interfaces

Cs/InN and Ba/InN interfaces were studied by UV photoelectron spectroscopy in the submonolayer coverage range for the first time. Normal photoemission spectra from the valence band and spectra from In 4d, Ba 5p, Ba 4d, and Cs 5p core levels were investigated in the excitation energy range of 60–800 eV. It was found that metallization of the interface and narrowing of the valence band is observed upon increasing coverage.     

Magnetic circular dichroism in Co 2p photoemission of Co/Cu(1 1 13): Separation of the fundamental spectra

We measured high-quality Co 2p magnetic circular dichroism (MCD) spectra in photoemission for > 5 ML Co films grown on Cu(1 1 13) using a “complete” experiment, where the sample magnetization and the light helicity vector were reversed separately. We show how the four measured spectra, M^±P^±, can be used to make new linear combinations, which correspond to the circular dichroism in the angular dependence (CDAD), magnetic linear dichroism in the angular dependence (MLDAD) and MCD spectra. The integrated signals of the MLDAD and CDAD can be used to estimate the error caused by the difference in the degrees of magnetization and light polarization, respectively, in the opposite alignments. The MCD signal integrated over the entire 2p region does not average to zero, as one would have expected from the sum rule for photoemission to a non-interacting continuum state. There is a strong MCD signal in the entire region between the 2p _3/2 and 2p _1/2 main lines with pronounced satellite structure. The differences between the measured and calculated results for an independent-particle and an atomic model indicate the presence of interatomic electron correlation effects and configurational mixing. Received 26 September 2000     

Angle-resolved polarization-dependent photoemission from Cu(100) and Cu(111): experiment and theory

Experimental angle-resolved photoemission spectra from Cu(111) and Cu(001) excited by linearly polarized light (21.2 eV) are compared with intensity results calculated by the “one step model” theory. Good overall agreement is obtained both for s- and p-polarized light assuming a classical macroscopic radiation field inside the crystal.     

Optimizing and characterizing grating efficiency for a soft X‐ray emission spectrometer

The efficiency of soft X‐ray diffraction gratings is studied using measurements and calculations based on the differential method with the S‐matrix propagation algorithm. New open‐source software is introduced for efficiency modelling that accounts for arbitrary groove profiles, such as those based on atomic force microscopy (AFM) measurements; the software also exploits multi‐core processors and high‐performance computing resources for faster calculations. Insights from these calculations, including a new principle of optimal incidence angle, are used to design a soft X‐ray emission spectrometer with high efficiency and high resolution for the REIXS beamline at the Canadian Light Source: a theoretical grating efficiency above 10% and resolving power E/ΔE > 2500 over the energy range from 100 eV to 1000 eV are achieved. The design also exploits an efficiency peak in the third diffraction order to provide a high‐resolution mode offering E/ΔE > 14000 at 280 eV, and E/ΔE > 10000 at 710 eV, with theoretical grating efficiencies from 2% to 5%. The manufactured gratings are characterized using AFM measurements of the grooves and diffractometer measurements of the efficiency as a function of wavelength. The measured and theoretical efficiency spectra are compared, and the discrepancies are explained by accounting for real‐world effects: groove geometry errors, oxidation and surface roughness. A curve‐fitting process is used to invert the calculations to predict grating parameters that match the calculated and measured efficiency spectra; the predicted blaze angles are found to agree closely with the AFM estimates, and a method of characterizing grating parameters that are difficult or impossible to measure directly is suggested.     

Angle-resolved resonant photoemission of Ni(100) and Ni(110) single crystals

We have studied the valence band photoemission spectra of Ni(100) and Ni(110) single crystals near the excitation threshold for 3p core electrons. The resonant behavior of the 6 eV satellite does not depend on both the surface orientation and the polarization of the electric vector of an incident light for excitation. These results indicate that the 6 eV satellite should be under little influence of spatial symmetry of the valence band. In the angle-resolved photoemission spectra of Ni(100), we have observed another broad feature near the 6 eV satellite. It shows the large energy dispersion and is interpreted as due to the interband transition. In Ni(110), we have observed the weak valence band satellites at binding energies of about 9.3 eV and 13.4 eV. They do not show well-defined resonance around the 3p threshold.     

Matrix‐isolation IR spectroscopy of R‐(+)‐3‐methylcyclopentanone in para‐hydrogen crystal

High‐resolution infrared (IR) spectra of R‐(+)‐3‐methylcyclopentanone (R3MCP) in para‐hydrogen (pH₂) crystal were recorded and compared with the corresponding IR spectra of R3MCP in Argon (Ar) isolation matrix as well as the IR spectra of the neat crystalline R3MCP at low deposition temperature of 4 ± 0.05 K. Moreover, IR spectra of R3MCP, hosted in pH₂ crystal, were recorded using a high‐resolution Fourier transform IR spectrometer as a function of sample concentration and over the range 10–300 ppm. Furthermore, density functional theory calculations of simulated IR spectra for the optimized geometries of R3MCP equatorial‐methyl and axial‐methyl conformers are compared with experimental spectra for the purpose of investigating molecular conformation. Upon comparison between theoretical and experimental IR spectra, vibrational modes arising from equatorial and axial conformers have been successfully assigned and related to the individual conformer's structure. Copyright © 2015 John Wiley & Sons, Ltd.     

Initial stage of oxidation of titanium

The electronic structure of titanium with different oxidation levels of the surface was studied by photoelectron spectroscopy and electron energy loss spectroscopy (EELS). The spectra of the valence band and the core level of Ti3p and EEL spectra were recorded for a titanium surface with oxidation exposures from 0.12 to 900 L at room temperature. In general, the titanium oxidation process is similar to that for zirconium, which was investigated earlier; however, certain features of the electronic structure that were not observed earlier were revealed for titanium. Even at high oxidation exposures of ∼1000 L, both O2p valence band and valence band corresponding to titanium metal states were observed. During consecutive oxidation, one can see four different positions of the Ti3p peak corresponding to titanium atoms with different valences. It is probable that, at the initial oxidation stage, islands of complex composition oxide were formed on the surface and grew into the bulk during further oxidation.     

Bond cutting in Cs‐doped tris(8‐hydroxyquinoline) aluminium

A series of Cs 4d and Al 2p spectra associated with valence‐band and cut‐off spectra have been used to characterize the interaction between caesium and tris(8‐hydroxyquinoline) aluminium (Alq₃) molecules in a Cs‐doped Alq₃ layer. The Cs 4d and Al 2p spectra were tuned to be very surface sensitive by selecting a photon energy of 120 eV at the National Synchrotron Radiation Research Center, Taiwan. A critical Cs concentration exists, above which a new Al 2p signal appears next to the Al 2p peak of Alq₃ in the lower binding‐energy side. The Al 2p signal was analyzed and assigned as being contributed from a mixture of Alq₂, Alq and Al. Experimental data supported the observation that bond cutting of Alq₃ by the doped Cs atoms occurred at high Cs doping concentration.     

2D degenerate electron gas at Ba/<Emphasis Type="Italic">n</Emphasis>-AlGaN and Ba/<Emphasis Type="Italic">n</Emphasis>-GaN interfaces

Ba/n-GaN(0001) and Ba/n-AlGaN(0001) interfaces were investigated for the first time by means of ultraviolet photoelectron spectroscopy. The spectra of the photoemission from a valence band along with the spectra of the core levels of Ga 3d, Al 2p, and Ba 4d were studied. The formation of a 2D degenerate electron gas (an accumulated layer on the n-GaN and n-AlGaN surfaces during adsorption of Ba atoms) was revealed.     

A novel computational strategy for the pKa estimation of drugs by non‐linear regression of multiwavelength spectrophotometric pH‐titration data exhibiting small spectral changes

A new computational procedure for the protonation model building of a multiwavelength and multivariate spectra treatment is proposed for the special case of small changes in spectra. The absorbance change Δ_i for the ith spectrum divided with the instrumental standard deviation s_inst(A) represents the signal‐to‐error ratio SER of the spectra studied. The determination of the number of chemical components in a mixture is the first important step for further quantitative analysis in all forms of spectral data treatment. Most index‐based methods of the factor analysis can always predict the correct number of components, and even the presence of a minor one, when the SER is higher than 10. The Wernimont–Kankare procedure in the program INDICES performs reliable determinations of the instrumental standard deviation of the spectrophotometer used s_inst(A), correctly predicts the number of light‐absorbing components present, and also solves ill‐defined problems with severe collinearity in spectra or very small changes in spectra. The mixed dissociation constants of three drugs, haemanthamine, lisuride, and losartan, including diprotic molecules at ionic strengths of I = 0.5 and 0.01 and at 25°C were determined using two different multiwavelength and multivariate treatments of the spectral data, SPECFIT32 and SQUAD(84) non‐linear regression analyses and INDICES factor analysis, even in the case of small absorbance changes in spectra. The dissociation constant pK_a was estimated by non‐linear regression of {pK_a, I} data at 25°C: for haemanthamine pK_a = 7.28(1) at I = 0.50, for lisuride pK_a = 7.86(1) and for losartan pK_a,1 = 3.60(1), pK_a,2 = 4.73(1) at I = 0.01. Goodness‐of‐fit tests for the various regression diagnostics enabled the reliability of the parameter estimates found to be proven. PALLAS and MARVIN predict pK_a being based on the structural formulae of the drug compounds in agreement with the experimental value. Copyright © 2007 John Wiley & Sons, Ltd.     

Photoemission investigation of the high temperature superconductors La2−x Sr x CuO4

Photoemission spectra of the La_2–x Sr _x CuO₄ system which recently has been demonstrated of being capable to produce high temperature (T _c >35 K) superconducting compounds are reported. The photoemission spectra of the basic system (La₂CuO₄) and of samples which contain up to 20% Sr are not significantly different. The density of states at the Fermi energy is small (smaller than that of metallic Cu) and the samples show a possible small shift of the Cu 2p lines towards the trivalent position with increasing tendency to superconductivity. From the Sr 3d spectra a considerable amount of oxygen defects coordinated to the Sr ions is estimated.     

Electronic structure of a Ba/<Emphasis Type="Italic">n</Emphasis>-AlGaN(0001) interface and the formation of a degenerate 2D electron gas

The electronic structure of ultrathin Ba/n-AlGaN(0001) interfaces has been investigated in situ in an ultra-high vacuum by the ultraviolet photoelectron spectroscopy method. The photoemission spectra from the n-AlGaN valence band and the spectra of the core levels Ga 3d, Al 2p, and Ba 4d have been studied under synchrotron excitation with photon energies of 60–400 eV. The modification of the spectra in the process of the formation of the Ba/n-AlGaN interface in the mode of the Ba submonolayer coverages has been revealed. It has been found that a decrease in the intensity in some spectral regions of the valence band is attributed to the interaction of the surface states of the AlGaN substrate with the Ba adatoms. It has been revealed that the interface formation results in the appearance of a new photoemission peak of the quasimetallic character at the Fermi level in the AlGaN bandgap. It has been established that the peak is due to the formation of the degenerate electron gas in the accumulation nanolayer induced by adsorption near the n-AlGaN surface.