Molecular Photoelectron Spectroscopy Research Articles

Investigation into atomistic reaction between abrasive and Co in H2O through ReaxFF MD and XPS

Co is expected to replace Cu as the next generation of interconnect metal material and plays an integral role in the field of integrated circuits (IC). However, the reaction mechanism behind Co chemical mechanical polishing is not yet clear. To fill these gaps, the following explorations have been conducted. Reactive force field molecular dynamics (ReaxFF MD) and X-ray photoelectron spectroscopy (XPS) were employed to investigate the atomistic reaction and removal underlying the cobalt (Co) chemical mechanical polishing (CMP) in an aqueous (H2O) environment. It demonstrates the adsorption of H2O onto the Co surface, resulting in the formation of Co-OH, Co-H2O, and other reaction products·H2O molecules also undergo reactions with the abrasive. Furthermore, the OH-terminated surface of the diamond abrasive can chemically interact with the Co substrate, resulting in the formation of C-O-Co bridge bonds. Additionally, the polishing process generates C-Co bonds. Both bonds contribute to the removal of Co atoms, although the former has a relatively smaller effect. A smaller gap between C and Co corresponds to a greater number of C-Co bonds and a faster attainment of dynamic equilibrium. Moreover, as the gap decreases, the normal and frictional force increase within a certain range. However, beyond a certain limit, the friction force decreases. This study aids in uncovering the atomic behavior at the interface during Co CMP and understanding the polishing mechanism.

Influence of tartaric acid on the electron transfer between oxyanions and lepidocrocite

Iron oxide minerals control the environmental behavior of trace elements. However, the potential effects of electron transfer directions by iron oxides between organic acids and trace elements remain unclear. This study investigates the redox capacity of tartaric acid (TA) with chromate (Cr(Ⅵ)) or arsenate (As(V)) on lepidocrocite (Lep) from the perspective of electron transfer. The results demonstrated the configurations of TA (bidentate binuclear (BB)), As(V) (BB), and Cr(Ⅵ) (BB and protonated monodentate binuclear (HMB)) on Lep. Frontier molecular orbital calculations and X-ray photoelectron spectroscopy (XPS) binding energy shifts further indicated different electron transfer directions between TA and the oxyanions on Lep. The iron of Lep might act as electron acceptors when TA is adsorbed, whereas the iron and oxygen of Lep act as electron donors when As(V) is adsorbed. The iron of Lep might accept electrons from its oxygen and subsequently transfer these electrons to Cr(Ⅵ). Macroscopic validation experiments showed the reduction of Cr(VI), whereas no reduction of As(V). The XPS analysis showed a peak shift, with the possible formation of As–Fe–TA ternary complexes and electron transfer on Lep. These findings indicate that mineral interfacial electron transfer considerably influences the transport and transformation of oxyanions.

High-Entropy Alloy with Mo-Coordination as Efficient Electrocatalyst for Oxygen Evolution Reaction

Electrochemical hydrolytic hydrogen production is the most promising method for renewable energy storage and conversion. However, the kinetic slow oxygen evolution reaction (OER) limits the development of water electrolysis at the anode. The state-of-the-art OER catalysts face a dilemma of high content of noble metals and low OER activities. Herein, a strategy for achieving efficient and stable high-entropy alloy (HEA) catalysts by Mo-coordination is reported. The earth-abundant FeCoNiMo HEA catalyst provides an overpotential as low as 250 mV at the current density of 10 mA cm–2 in alkaline medium, which is 89 mV lower than that of state-of-the-art IrO2. The turnover frequency of 0.051 s–1 at the overpotential of 300 mV of FeCoNiMo HEA is 3 times higher than that of commercial IrO2 catalyst and even 11 times higher than that of the FeCoNi alloy without Mo-coordination. Importantly, the FeCoNiMo HEA exhibits high OER stability at a high current density of 100 mA cm–2. Methanol molecular probe experiment and X-ray photoelectron spectroscopy analyses suggest that the electrons of Mo transfer to Fe, Co, and Ni in the FeCoNiMo HEA catalyst, which leads to a weakened OH* bonding and, as a result, enhanced OER performance of the FeCoNiMo HEA catalyst. Consistent with the methanol molecular probe analysis, the real-time OER kinetic simulation reveals that the coordination of Mo within FeCoNi can speed up the rate-determining OH* deprotonation step of OER. Our finding opens up a routine for designing efficient cost-effective electrocatalysts for OER, which could facilitate discoveries in OER catalysts.

Theoretical and experimental investigations into the pyrolysis mechanisms of silicon-modified phenolic resin under high temperatures

ReaxFF molecular dynamics (ReaxFF-MD) simulations and X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman, Fourier transform infrared spectroscopy (FT-IR), 29Si NMR were used to investigate the temperature-dependent pyrolysis gas release behavior, dynamic evolution of microstructure, and fundamental carbonization mechanism of silicon-modified phenolic resin (SiPR). An improved and effective algorithm for model building was used to construct the cross-linked SiPR simulation model by considering three reactions in the actual experimental cross-linking process with adjustable occurrence rates. Tracking and analysis of the structures showed that with the continuous release of pyrolysis gas, the residual Si and C-containing components decomposed, rearranged, and aggregated into different phase structures. The Si-units agglomerated and underwent phase separation stages. The carbonization process was divided into three periods: initial aromatization, merging and flattening, and residual healing. These findings may shed light on the polysilicon phase distribution and carbonization mechanism of SiPR.

Novel adsorption-photocatalysis integrated bismuth tungstate modified layered mesoporous titanium dioxide (Bi2WO6/LM-TiO2) composites

Using cetyltrimethylammonium bromide (CTAB) as the soft template and titanium sulfate as the titanium source, the layered mesoporous TiO2 (LM-TiO2) was prepared by the novel precipitation-peptization method, then bismuth tungstate was synthesized and coupled with layered mesoporous titanium dioxide by the hydrothermal process to obtain adsorption-photocatalysis integrated Bi2WO6/LM-TiO2 composites. The surface morphology, transmission morphology and elemental mapping, particle size, crystal phase composition, ultraviolet absorption band, fluorescence intensity, functional group structure, element composition and valence state of the samples were characterized using scanning electron microscopy (SEM), transmission electron microscope (TEM), laser particle size analyzer, X-ray diffraction (XRD), ultraviolet visible absorption spectrum (UV–Vis-Abs), Molecular fluorescence spectrophotometer (PL) and X-Ray photoelectron spectroscopy (XPS), respectively. Taking methyl orange as the target substance, the adsorption and photocatalytic performances of the samples were studied. The results indicate that Bi2WO6/LM-TiO2 composites have excellent adsorption and photocatalytic degradation performances. When irradiated with a 500 W metal halide lamp for 20 min, the removal rate of methyl orange by 8% Bi2WO6/LM-TiO2 reaches 93.60% which is greatly improved compared with simple LM-TiO2, and is twice as that of P25. By coupling LM-TiO2 with Bi2WO6, the composites show a spherical structure, and the crystallinity does not change significantly. Moreover, the light absorption band edge has a certain red shift and the photogenerated electron-hole recombination is restrained, thereby improving the photocatalytic performance.

Highly efficient interface stabilization for ambient-temperature quasi-solid-state sodium metal batteries

Solid-state sodium (Na) batteries (SSSBs) using sulfide-based solid electrolytes (SSEs) hold tremendous promise due to their high theoretical specific capacity, enhanced safety and abundant resources. However, detrimental interfacial issues between SSEs and Na metal present a major challenge to the advancement of sulfide-based SSSBs. To address interfacial issues, we demonstrate an efficient approach by incorporating an ionic liquid electrolyte ((PYR/Na)TFSI) as interlayer to stabilize the Na metal/SSE interface. The presence of the (PYR/Na)TFSI interlayer enables the formation of a stable solid electrolyte interphase (SEI) to prevent the harmful reactions and inhibit Na dendrites. Combination of ab initio molecular dynamics simulations and X-ray photoelectron spectroscopy reveale that this stable SEI is largely composed of reduced products of TFSI−, such as NaF and CF3. As a result, the symmetric cells exhibited stable Na plating/striping cycling for 300 h at 0.1 mA cm−2. In addition, FeS2||Na quasi-solid-state batteries delivered an impressive specific capacity of over 300 mAh g−1 under the current density of 20 mA g−1 at room temperature. Under a higher current density (100 mA g−1), such batteries performed with long-term cycling stability and maintained a specific capacity of around 103 mAh g−1 after 330 cycles. This work demonstrates the novel perspective of using an ionic liquid interlayer to address interfacial issues, contributing to the advancement of high-performance SSSBs for the next-generation energy storage systems.

Structure and stability of 7-mercapto-4-methylcoumarin self-assembled monolayers on gold: an experimental and computational analysis.

Self-assembled monolayers (SAM) of 7-mercapto-4-methylcoumarin (MMC) on a flat gold surface were studied by molecular dynamics (MD) simulations, reference-free grazing incidence X-ray fluorescence (GIXRF) and X-ray photoelectron spectroscopy (XPS), to determine the maximum monolayer density and to investigate the nature of the molecule/surface interface. In particular, the protonation state of the sulfur atom upon adsorption was analyzed, since some recent literature presented evidence for physisorbed thiols (preserving the S-H bond), unlike the common picture of chemisorbed thiyls (losing the hydrogen). MD with a specifically tailored force field was used to simulate either thiol or thiyl monolayers with increasing number of molecules, to determine the maximum dynamically stable densities. This result was refined by computing the monolayer chemical potential as a function of the density with the bennet acceptance ratio method, based again on MD simulations. The monolayer density was also measured with GIXRF, which provided the absolute quantification of the number of sulfur atoms in a dense self-assembled monolayer (SAM) on flat gold surfaces. The sulfur core level binding energies in the same monolayers were measured by XPS, fitting the recorded spectra with the binding energies proposed in the literature for free or adsorbed thiols and thiyls, to get insight on the nature of the molecular species present in the layer. The comparison of theoretical and experimental SAM densities, and the XPS analysis strongly support the picture of a monolayer formed by chemisorbed, dissociated thiyls.

Trends in angle-resolved molecular photoelectron spectroscopy.

The field of angle-resolved molecular photoelectron spectroscopy is reviewed, with emphasis on foundations and most recent applications in different regimes of light-matter interaction. The basic formalism underlying one-photon electron angular distributions is presented, from the primary molecular frame (MF) photoemission i.e. emission from fully oriented molecules to laboratory frame (LF) observables produced from randomly oriented targets, extensions to multiphoton and strong field processes being briefly described, followed by a survey of current quantum mechanical computational approaches. The description of experimental developments is focused on the advancements in two major instrumentation fields for angle-resolved PES of molecules in the last two decades, namely charged-particle imaging spectrometers and adiabatically or impulsively laser-induced molecular alignment, together with their interplay with the remarkable characteristics achieved nowadays by the ionizing light sources and the challenging control of complex molecules in the gas phase. Aspects and applications of LF angular observables from unoriented targets are presented, with contemporary applications, especially as probes of the target electronic structure, including higher angular observables, in particular photoelectron circular dichroism (PECD) from chiral molecules, which is confirmed as a powerful chiral technique, and higher terms arising from multiphoton or non-dipole terms. Molecular frame photoelectron angular distributions (MFPADs), which stand out as the most complete observables of molecular photoionization stereodynamics in different excitation regimes, now broadly extended to characterize molecular structure and dynamics, are then discussed stemming from fully oriented molecules tackled by electron-ion momentum coincidence techniques, or from laser aligned samples. Finally, novel developments and challenging perspectives, notably the implementation of PAD in time-resolved schemes at ultrashort time scales, high energy, and high intensity regimes are drawn.

Effect of humidity on the microstructure and energy storage properties of polyetherimide

The linear polymer, polyetherimide (PEI), has attracted much attention in recent years due to its high energy storage efficiency and high operating temperature. In this work, the effect of humidity on the relevant properties of PEI is investigated by changing the ambient humidity during electrostatic spinning. The results show that humidity affects the microscopic morphology of PEI after spinning and the dielectric energy storage properties of PEI films. Microstructure images show that the humidity of the spinning environment not only affects the morphology of the PEI filament, but also has an effect on the surface morphology of the PEI film after hot pressing. The experimental test results demonstrate that humidity has a significant effect on the energy storage performance. The reasons for this change were analyzed by molecular dynamics and x-ray photoelectron spectroscopy (XPS). It was found that the attraction of hydroxyl groups may hinder the rotation of the phthalimide rings reducing the polarization rate causing a decrease in polarization.

Thin solid electrolyte interface on chemically bonded Sb2Te3/CNT composite anodes for high performance sodium ion full cells

Nanostructured metal chalcogenides (MCs) and their composites are studied for high performance sodium-ion batteries (SIBs). Herein, we report the assembly of an emerging MC, Sb2Te3, with functionalized carbon nanotubes (CNTs) to form composite anodes. The role of oxygenated functional groups on CNTs in fostering the chemical interactions with Sb2Te3 for enhanced structural integrity of electrodes is elucidated by density functional theory combined with ab-initio molecular dynamics simulations and X-ray photoelectron spectroscopy analysis. Remarkably, cryogenic transmission electron microscopy (TEM) analysis reveals a uniform and thin solid electrolyte interface (SEI) layer of ~19.1 nm on the Sb2Te3/CNT composite while the neat Sb2Te3 presents an irregular and ~67.3 nm thick SEI. The ex-situ X-ray diffraction (XRD) and ex-situ/in-situ TEM analyses offer mechanistic explanations of phase transition and volume changes during sodiation. The Sb2Te3/CNT composite electrode with an optimal content of 10 wt% CNTs delivers excellent reversible gravimetric and volumetric capacities of 422 mA h g−1 and 1232 mA h cm−3, respectively, at 100 mA g−1 with ~97.5% capacity retention after 300 cycles. The excellent high-rate capability of 318 mA h g−1 at 6400 mA g−1 corroborates the structural robustness of the composite electrode. Sodium-ion full cells (SIFCs) are assembled by pairing the above anode with a Na3V2(PO4)2F3 cathode, which exhibit remarkable energy density of ~229 Wh kg−1 at 0.5 C and excellent cyclic stability of over 71% and 66% capacity retention at 5 C and 10 C, respectively, after 200 cycles. Even at 40 C, an ultrahigh power density of 5384 W kg−1 is delivered. Furthermore, the pouch-type SIFCs prove excellent flexibility with ~85% capacity retention after 1000 bending cycles and satisfactory operation under temperatures ranging from 40 to −20 °C. The design strategy developed here can also be employed to other electrode materials to achieve better SEI stability and excellent Na storage performance.

Preparation and Photocatalytic Properties of CdS/F–TiO2 Composites

F–TiO2 was prepared by a simple precipitation method using titanium sulfate as the titanium source, hydrogen fluoride as the fluorine source and ammonia as the precipitant. CdS/F–TiO2 composites were prepared by hydrothermal synthesis of CdS and F–TiO2. The surface morphology, crystal phase composition, ultraviolet absorption band, fluorescence intensity, element composition, valence state, specific surface and pore structure of the samples were characterized by using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), ultraviolet visible absorption spectrum (UV-Vis-Abs), Molecular fluorescence spectrophotometer (PL) and X-Ray photoelectron spectroscopy (XPS) and Surface area analyzer (BET), respectively. The effects of the dosage of the photocatalyst, pH value, the concentration of methyl orange and the addition of H2O2 on the photocatalytic performance were investigated with methyl orange solution as the target degradation product. The results showed the optimum condition for photodegradation of methyl orange by 1% CdS/F–TiO2 is that the pH value, the solid-liquid ratio, the concentration of methyl orange and the dosage of H2O2 is 2, 2 g/L, 10 mg/L and 3%, respectively. Under the same conditions, the degradation rate of methyl orange by 1% CdS/F–TiO2 was 93.36% when 300 W metal halide lamp was irradiated for 20 minutes, which was significantly higher than that of F–TiO2. CdS has a significant effect on the morphology, crystallinity, grain size and the compound probability of electrons and holes after the F–TiO2 modification. The composite causes a significant red shift at the edge of the F–TiO2 light absorption band. The photocatalytic degradation of methyl orange by 1% CdS/F–TiO2 follows the Langmuir-Hinshelwood first-order kinetic model.

Tuning Sodium Interfacial Chemistry with Mixed-Anion Ionic Liquid Electrolytes.

The interphase layer that forms on either the anode or the cathode is considered to be one of the critical components of a high performing battery. This solid-electrolyte interphase (SEI) layer determines the stability of the electrode in the presence of a given electrolyte as well as the internal resistance of a battery, and hence the overpotential of a cell. In the case of lithium ion batteries where carbonate based electrolytes are used, additives including hexafluorophosphate (PF6), bis-trifluoromethylsulfonimide (TFSI), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI), and fluorosulfonimde (FSI) are used to obtain favorable SEI layers. Ionic liquids and salts based on anions containing nitrile groups, including dicyanamide (DCA), offer a less expensive alternative to a fluorinated anion and have also been shown to support stable electrochemistry in lithium and sodium systems. However, longer term cycling leads to the eventual passivation of the electrode, presumed to be due to the instability of the DCA anion. We herein consider the use of a fluorinated anion to control the interfacial electrochemistry and provide a more stable SEI in DCA ILs. We investigate the addition of NaDCA, NaFSI, NaTFSI, and NaFTFSI to the methylpropylpyrrolidinium dicyanamide ([C3mpyr]DCA) ionic liquid. NaFSI was found to generate a more stable SEI layer, as evidenced by extended symmetric cell cycling, while the TFSI and FTFSI salts both lead to thicker, highly passivating surfaces. We use molecular dynamics, infrared spectroscopy and X-ray photoelectron spectroscopy to interrogate and discuss the influence of the anion on the bulk electrolyte, the interfacial electrolyte structure, and the formation of the SEI layer, in order to rationalize the contrasting electrochemical observations.

Role of Inorganic Surface Layer on Solid Electrolyte Interphase Evolution at Li-Metal Anodes.

Lithium metal is an ideal anode for rechargeable lithium-battery technology. However, the extreme reactivity of Li metal with electrolytes leads to solid electrolyte interphase (SEI) layers that often impede Li+ transport across interfaces. The challenge is to predict the chemical, structural, and topographical heterogeneities of SEI layers arising from a multitude of interfacial constituents. Traditionally, the pathways and products of electrolyte decomposition processes were analyzed with the basic and simplifying presumption of an initial pristine Li-metal surface. However, ubiquitous inorganic passivation layers on Li metal can reduce electronic charge transfer to the electrolyte and significantly alter the SEI layer evolution. In this study, we analyzed the effect of nanometric Li2O, LiOH, and Li2CO3 as surface passivation layers on the interfacial reactivity of Li metal, using ab initio molecular dynamics (AIMD) calculations and X-ray photoelectron spectroscopy (XPS) measurements. These nanometric layers impede the electronic charge transfer to the electrolyte and thereby provide some degree of passivation (compared to pristine lithium metal) by altering the redox-based decomposition process. The Li2O, LiOH, and Li2CO3 layers admit varying levels of electron transfer from a Li-metal slab and subsequent storage of the electronic charges within their structures. As a result, their ability to transfer electrons to the electrolyte molecules, as well as the extent of decomposition of bis(trifluoromethanesulfonyl)imide anions, is significantly reduced compared to similar processes on pristine Li metal. The XPS experiments revealed that when Li2O is the major component on the altered surface, LiF phases formed to a greater extent. The presence of a dominant LiOH layer, however, results in enhanced sulfur decomposition processes. From AIMD studies, these observations can be explained based on the calculated quantities of electronic charge transfer found for each of the passivating films.

Advances in threshold photoelectron spectroscopy (TPES) and threshold photoelectron photoion coincidence (TPEPICO).

The history and evolution of molecular threshold photoelectron spectroscopy and threshold photoelectron photoion coincidence spectroscopy (TPEPICO) over the last fifty years are reviewed. Emphasis is placed on instrumentation and the extraction of dynamical information about energy selected ion dissociation, not on the detailed spectroscopy of certain molecules. Three important advances have expanded greatly the power of the technique, and permitted its implementation on modern synchrotron radiation beamlines. The use of velocity focusing of threshold electrons onto an imaging detector in the 1990s simultaneously improved the sensitivity and electron energy resolution, and also facilitated the subtraction of hot electron background in both threshold electron spectroscopy and TPEPICO studies. The development of multi-start multi-stop collection detectors for both electrons and ions in the 2000s permitted the use of the full intensity of modern synchrotron radiation thereby greatly improving the signal-to-noise ratio. Finally, recent developments involving imaging electrons in a range of energies as well as ions onto separate position-sensitive detectors has further improved the collection sensitivity so that low density samples found in a variety of studies can be investigated. As a result, photoelectron photoion coincidence spectroscopy is now well positioned to address a range of challenging problems that include the quantitative determination of compositions of isomer mixtures, and the detection and spectroscopy of free radicals produced in pyrolysis or discharge sources as well as in combustion studies.

Interaction of Al with O2 exposed Mo2BC

A Mo2BC(040) surface was exposed to O2. The gas interaction was investigated using ab initio molecular dynamics and X-ray photoelectron spectroscopy (XPS) of air exposed surfaces. The calculations suggest that the most dominating physical mechanism is dissociative O2 adsorption whereby MoO, OMoO and Mo2CO bond formation is observed. To validate these results, Mo2BC thin films were synthesized utilizing high power pulsed magnetron sputtering and air exposed surfaces were probed by XPS. MoO2 and MoO3 bond formation is observed and is consistent with here obtained ab initio data. Additionally, the interfacial interactions of O2 exposed Mo2BC(040) surface with an Al nonamer is studied with ab initio molecular dynamics to describe on the atomic scale the interaction between this surface and Al to mimic the interface present during cold forming processes of Al based alloys. The Al nonamer was disrupted and Al forms chemical bonds with oxygen contained in the O2 exposed Mo2BC(040) surface. Based on the comparison of here calculated adsorption energy with literature data, AlAl bonds are shown to be significantly weaker than the AlO bonds formed across the interface. Hence, AlAl bond rupture is expected for a mechanically loaded interface. Therefore the adhesion of a residual Al on the native oxide layer is predicted. This is consistent with experimental observations. The data presented here may also be relevant for other oxygen containing surfaces in a contact with Al or Al based alloys for example during forming operations.

Surface behavior of amphiphiles in aqueous solution: a comparison between different pentanol isomers.

Position isomerism is ubiquitous in atmospheric oxidation reactions. Therefore, we have compared surface-active oxygenated amphiphilic isomers (1- and 3-pentanol) at the aqueous surface with surface- and chemically sensitive X-ray photoelectron spectroscopy (XPS), which reveals information about the surface structure on a molecular level. The experimental data are complemented with molecular dynamics (MD) simulations. A concentration-dependent orientation and solvation of the amphiphiles at the aqueous surface is observed. At bulk concentrations as low as around 100 mM, a monolayer starts to form for both isomers, with the hydroxyl groups pointing towards the bulk water and the alkyl chains pointing towards the vacuum. The monolayer (ML) packing density of 3-pentanol is approx. 70% of the one observed for 1-pentanol, with a molar surface concentration that is approx. 90 times higher than the bulk concentration for both molecules. The molecular area at ML coverage (≈100 mM) was calculated to be around 32 ± 2 Å(2) per molecule for 1-pentanol and around 46 ± 2 Å(2) per molecule for 3-pentanol, which results in a higher surface concentration (molecules per cm(2)) for the linear isomer. In general we conclude therefore that isomers - with comparable surface activities - that have smaller molecular areas will be more abundant at the interface in comparison to isomers with larger molecular areas, which might be of crucial importance for the understanding of key properties of aerosols, such as evaporation and uptake capabilities as well as their reactivity.

Adsorption of uranyl ions on kaolinite, montmorillonite, humic acid and composite clay material

Adsorption of uranyl ions onto kaolinite, montmorillonite, humic acid and composite clay material (both clays and humic acid) was studied by measuring the system response to clay suspensions (pre-equilibrated with or without uranyl) and to perturbations of the solution chemistry. Adsorption behavior of selected materials under the frame of batch experiments was tested at high uranyl concentrations (6–1170μg/mL; 2.5×10−2 to 4.9μM), whereas that under flow through continuous stirred reactor experiments was tested at low concentrations (1.00×10−4 to 1.18×10−4M). Both experiments were developed at pH4.5 and ionic strength 0.2mM. The adsorption experiments follow a Langmuir isotherm model with a good correlation coefficient (R2>0.97). The calculated amount of adsorbed and desorbed uranyl was carried out by numeric integration of the experimental data, whereas the desorption rates were determined from the breakthrough curve experiments. Kaolinite with highly disordered structure adsorbed less uranyl (3.86×10−6mol/g) than well-ordered kaolinite (1.76×10−5mol/g). Higher amount of uranyl was adsorbed by montmorillonite (3.60×10−5mol/g) and only half of adsorbed amount was desorbed (1.85×10−5mol/g). The molecular interactions between kaolinite, montmorillonite, humic acid, composite material and saturated uranyl ion solutions were studied by molecular fluorescence, infrared and X-ray photoelectron spectroscopy. The Stern–Volmer constant obtained for montmorillonite (2.6×103M−1) is higher than for kaolinite (0.3×103M−1). Molecular vibrations of SiO stretching and AlOH bending related to hydroxylated groups (SiOH or AlOH) of kaolinite and montmorillonite show structural changes when uranyl ions are adsorbed. X-ray photoelectron spectroscopy shows that the U 4f7/2 core level signals occur at 380.5eV in either kaolinite or montmorillonite that resulted from the interaction of aluminol surface sites with the (UO2)3(OH)5+.

Atomic selectivity in dissociative electron attachment to dihalobenzenes

We investigated electron attachment to three dihalobenzene molecules, bromochlorobenzene (BCB), bromoiodobenzene (BIB) and chloroiodobenzene (CIB), by molecular beam photoelectron spectroscopy. The most prominent product of electron attachment in the anion mass spectra was the atomic fragment of the less electronegative halogen of the two, i.e., Br(-) for BCB and I(-) for BIB and CIB. Photoelectron spectroscopy and ab initio calculations suggested that the approaching electron prefers to attack the less electronegative atom, a seemingly counterintuitive finding but consistent with the mass spectrometric result. For the iodine-containing species BIB and CIB, the photoelectron spectrum consists of bands from both the molecular anion and atomic I(-), the latter of which is produced by photodissociation of the former. Molecular orbital analysis revealed that a large degree of orbital energy reordering takes place upon electron attachment. These phenomena were shown to be readily explained by simple molecular orbital theory and the electronegativity of the halogen atoms.

Collective hydrogen-bond dynamics dictates the electronic structure of aqueous I3−

The molecular and electronic structures of aqueous I3(-) and I(-) ions have been investigated through ab initio molecular dynamics (MD) simulations and photoelectron (PE) spectroscopy of the iodine 4d core levels. Against the background of the theoretical simulations, data from our I4d PE measurements are shown to contain evidence of coupled solute-solvent dynamics. The MD simulations reveal large amplitude fluctuations in the I-I distances, which couple to the collective rearrangement of the hydrogen bonding network around the I3(-) ion. Due to the high polarizability of the I3(-) ion, the asymmetric I-I vibration reaches partially dissociated configurations, for which the electronic structure resembles that of I2 + I(-). The charge localization in the I3(-) ion is found to be moderated by hydrogen-bonding. As seen in the PE spectrum, these soft molecular vibrations are important for the electronic properties of the I3(-) ion in solution and may play an important role in its electrochemical function.

Study of the Initial Stage of Solid Electrolyte Interphase Formation upon Chemical Reaction of Lithium Metal andN-Methyl-N-Propyl-Pyrrolidinium-Bis(Fluorosulfonyl)Imide

Chemical reaction studies of N-methyl-N-propyl-pyrrolidinium- bis(fluorosulfonyl)imide-based ionic liquid with the lithium metal surface were performed using ab initio molecular dynamics (aMD) simulations and X-ray Photoelectron Spectroscopy (XPS). The molecular dynamics simulations showed rapid and spontaneous decomposition of the ionic liquid anion, with subsequent formation of long-lived species such as lithium fluoride. The simulations also revealed the cation to retain its structure by generally moving away from the lithium surface. The XPS experiments showed evidence of decomposition of the anion, consistent with the aMD simulations and also of cation decomposition and it is envisaged that this is due to the longer time scale for the XPS experiment compared to the time scale of the aMD simulation. Overall experimental results confirm the majority of species suggested by the simulation. The rapid chemical decomposition of the ionic liquid was shown to form a solid electrolyte interphase composed of the breakdown products of the ionic liquid components in the absence of an applied voltage.