Gas Phase Environment Research Articles

Defect Chemistry of Titanium Dioxide (Rutile). Progress Toward Sustainable Energy.

This work, which overviews defect chemistry of TiO2 (rutile), is focused on atomic-size structural defects that are thermodynamically reversible. Here it is shown that thermodynamics can be used in defect engineering of TiO2-based energy materials, such as photoelectrodes and photocatalysts. We show that surface segregation of defects leads to the building-up of new surface structures that are responsible for reactivity. Since rational design of surface properties requires in situ surface characterization in operational conditions, expansion of bulk defect chemistry to surface defect chemistry requires a defect-related surface-sensitive tool for in situ monitoring of defect-related properties at elevated temperatures corresponding to defect equilibria and in a controlled gas-phase environment. Here we show that the high-temperature electron probe is a defect-related surface-sensitive tool that is uniquely positioned to aid surface defect engineering and determine unequivocal surface properties. The related applied aspects are considered for photoelectrochemical water splitting and the performance of solid oxide fuel cells. Here we report that trail-blazing studies on in situ surface monitoring of TiO2 during gas/solid equilibration, along with in situ characterization of surface semiconducting properties, leads to the discovery of a segregation-induced low-dimensional surface structure that is responsible for stable performance of oxide semiconductors, such as TiO2, in operational conditions.

Effect of relative humidity on passive spore release from substrate surfaces

Fungal spores are abundant in ambient air and exposure to this type of bioaerosols are found to cause significant health and climatic effects. In this study, we investigated the influence of air relative humidity (RH) on the passive release of spores from solid substrates. Preliminary investigations into the effect of RH on fungal spore release indicated an increase in spore flux with reduced air RH. The change in spore emission flux occurred very quickly in response to a change in ambient RH. To verify the hypothesis of extremely rapid drying under lower RH, experiments were conducted using a quartz crystal microbalance with dissipation (QCM-D) to understand the timescales of spore moisture uptake and drying. The analysis of mass transfer of water to and from the spores indicated that the bulk of the transfer occurred within a minute of exposure to any RH. The effect of the ambient RH was explained using a mathematical model with the spotlight on the parameter, E, that represented the energy required to aerosolise one spore. This study demonstrates the application of QCM-D to study interaction between ambient aerosol particles and various vapor phase and gas phase environments. The study enhances the overall understanding and capability to characterise passive fungal spore release under varying humidity conditions in the natural environment.

Formation of acetonitrile (CH3CN) under cold interstellar, tropospheric and combustion mediums

The knowledge of the formation of gas-phase carcinogenic acetonitrile (CH3CN) is limited in interstellar, troposphere, and combustion mediums; thus, its formation and fate are of great importance for all these gas-phase environments when accessing its toxicity and its wide range of applications. In this work, we propose a mechanism for the formation of CH3CN from the reaction of OH/O2 on ethanimine (CH3CH=NH) using ab initio/Density Functional Theory (DFT) potential energy surface in combination with microcanonical variational transition state theory (µVTST) and Ramsperger–Kassel–Marcus (RRKM)/master equation (ME) simulation to predict the rate constants and branching fraction in the temperature range of 100 K to 1000 K and pressure range of 0.0001 bar to 100 bar. The reaction starts with cis (Z) and trans (E) CH3CH=NH isomer with OH radical followed by spontaneous formation via pre-reactive complex, forming the carbon and nitrogen-centered radicals. The O2 radical then attacks the carbon and nitrogen-centered radicals to form acetonitrile (CH3CN) and HO2 radicals. The results show that N–H and C–H dominate the H-atoms abstraction by OH radicals is similar to its isoelectronic analogous reaction system, i.e., CH3CHO + OH/O2 and CH3CHCH2 + OH/O2 and similar to methanimine (CH2NH) systems. The calculated rate constants for OH-initiated oxidation of CH3CH=NH are in the range of ~ 10–11 cm3 molecule−1 s−1 (at 300 K) and are in very good agreement with previous experimental values of its isoelectronic reaction system. The atmospheric lifetime due to the loss of CH3CHNH by OH radical (10 to 11 h) is in very good agreement with the similar pollutants in the troposphere temperature range between 200 and 320 K. The results indicate that its contribution to global warming is negligible. However, the formation of products such as CH3CN may interact with other atmospheric species, which could lead to the production of potentially hazardous compounds such as cyanogen (N2C2) and hydrogen cyanide (HCN).

Quantum computations on a new neural network potential for the proton-bound noble-gas Ar[formula omitted]H[formula omitted] complex: Isotopic effects

High-quality data-driven potentials were developed aiming to predict rovibrational traits and analyze the influence of the isotopic substitution on the molecular spectroscopic properties of Ar2H+. Neural networks machine-learning approaches trained on CCSD(T)/CBS datasets were implemented. Our full-dimensional quantum MCTDH results were discussed in comparison with experimental data in gas phase and solid matrix environments, as well as against theoretical estimates available. The new data indicate that both fundamental and progression bands are dominantly driven by the strength and shape of the underlying interactions. Our simulations could enable the spectroscopic characterization of these species, assisting investigations for their astrophysical observation.

High Mass Transfer Rate in Electrocatalytic Hydrogen Evolution Achieved with Efficient Quasi-Gas Phase System.

The adhesion of H2 bubbles on the electrode surface is one of the main factors limiting the performance of H2 evolution of electrolytic water, especially at high current density. To overcome this problem, here a "quasi-gas phase" electrolytic water reaction system based on capillary effect is proposed for the first time to improve the mass transfer efficiency of H2. The typical feature of this reaction system is that the main site of H2 evolution reaction is transferred from the bulk aqueous solution to the gas phase environment above the bulk aqueous solution, thus effectively inhibiting the aggregation of H2 bubbles and reducing the resistance of their diffusion away. Electrochemical test results show that the proposed quasi-gas phase system can significantly reduce the potential required in H2 evolution reaction process at high current density compared with the conventional electrolytic reaction system. Specifically, the overpotential potential is reduced by 0.31 V when the H2 evolution current density of 250 mA cm-2 is achieved.

High Mass Transfer Rate in Electrocatalytic Hydrogen Evolution Achieved with Efficient Quasi‐Gas Phase System

The adhesion of H2 bubbles on the electrode surface is one of the main factors limiting the performance of H2 evolution of electrolytic water, especially at high current density. To overcome this problem, here a "quasi‐gas phase" electrolytic water reaction system based on capillary effect is proposed for the first time to improve the mass transfer efficiency of H2. The typical feature of this reaction system is that the main site of H2 evolution reaction is transferred from the bulk aqueous solution to the gas phase environment above the bulk aqueous solution, thus effectively inhibiting the aggregation of H2 bubbles and reducing the resistance of their diffusion away. Electrochemical test results show that the proposed quasi‐gas phase system can significantly reduce the potential required in H2 evolution reaction process at high current density compared with the conventional electrolytic reaction system. Specifically, the overpotential potential is reduced by 0.31 V when the H2 evolution current density of 250 mA cm‐2 is achieved.

The kinetics of droplet wetting gas hydrate surfaces regulated by anti-agglomerant monolayers: Insights from molecular dynamics study

Anti-agglomerants (AAs) have become a promising strategy for mitigating gas hydrate risks in hydrocarbon transport systems. However, a notable limitation of AAs is their diminished effectiveness in systems with high water content. The density of the AA monolayer is a critical factor influencing the coalescence and agglomeration of hydrate particles with water droplets, but the mechanisms driving these effects remain largely unknown. In this study, molecular dynamics (MD) simulations were employed to explore the anti-wetting performance and interaction properties of Cocamide Monoethanolamine (CMEA) monolayers at varying densities on hydrate surfaces. The results indicate that in systems with low-density monolayers, CMEA molecules exhibit high degrees of freedom and increased fluctuation frequencies, allowing the water molecules of droplet to penetrate the monolayer and rapidly wet the hydrate surface. In contrast, high-density monolayer configurations show properties that hinder droplet wetting on hydrate surfaces and inhibit hydrate growth. Further investigation into the adsorption behavior of CMEA molecules on hydrate surfaces highlights the substantial impact of the solution phase on adsorption free energy, with gas-phase environments enhancing the binding strength between CMEA molecules and hydrate surfaces. These molecular insights offer valuable observations regarding the structural adaptability of AA monolayers during droplet permeation and wetting processes, providing critical information for understanding the broader interactions between anti-agglomerant molecules and hydrates.

Virtual screening, molecular docking, MD simulation studies, DFT calculations, ADMET, and drug likeness of Diaza-adamantane as potential MAPKERK inhibitors.

Introduction: Multiple sclerosis (MS) is an autoimmune and inflammatory disease that destroys the protective coating of central nervous system (CNS) nerve fibers and affects over 2.8 million people worldwide. Despite several studies on new therapeutic targets and lead compounds, MS disease has limited treatment options. This condition may be caused by a complicated interaction of environmental and genetic variables. Studies showed that MS-associated microglial cells' increased MAPKERK activity may cause CNS inflammation and oligodendrocyte damage. Thus, screening for lead compounds that inhibit MAPKERK may protect brain cells and slow disease progression. Methods: The study aims to discover compounds that may inhibit MAPKERK as a novel approach for protecting the nervous system in managing MS. The study includes in silico methods, such as virtual screening, molecular docking, Density-functional theory (DFT) investigations (using the B3LYP/6-31++G(d,p) basis set in a gas phase environment), drug likeness scores, and molecular dynamic (MD) simulations. Results and Discussion:During the docking process with the MAPKERK protein, it was shown that the ligand L12 receptor had the best binding affinity, with a docking score of -6.18kcal/mol. To investigate the stability of the binding, a 100ns MD simulation was performed on the complex formed by the MAPKERK protein and L12. The receptor-ligand combination exhibited significant stability throughout the duration of the MD simulation. Additionally, the pharmacokinetic and drug-likeness properties of these ligands suggest that they have the potential to be considered viable candidates for future development in MS management.

The Magnesium Dication and Water Synergistically Promote the Protonolysis of Two of the B-C Bonds in the Tetraphenylborate Anion.

Analytes are sampled from both solution phase and gas-phase environments during the ESI process, and thus, the mass spectrum that is measured can reflect both solution and gas-phase conditions. In the gas-phase regime, ion-molecule reactions can influence the types of ions that are observed. Herein, the synergistic effects of a Lewis acid (Mg2+) and background water are shown to lead to protonolysis of two of the B-C bonds of the tetraphenylborate ion in the gas phase, giving rise to different ions at different reaction times in ESI-MS/MS experiments in a linear ion trap mass spectrometer. At short reaction times (1 ms), the expected adduct [Mg(BPh4)]+ is observed. At 10 ms, [(HO)Mg(BPh3)]+ and [(HO)2Mg(BPh2)]+ are observed. At 100 ms, the water adducts [(HO)2Mg(BPh2)(H2O)]+ and [(HO)2Mg(BPh2)(H2O)2]+ appear, and these become the dominant ions at longer reaction times. DFT calculations provide a plausible explanation as to why only [(HO)Mg(BPh3)]+ and [(HO)2Mg(BPh2)]+ but not [(HO)3Mg(BPh)]+ are observed.

Gas-phase Molecules in Protoplanetary Nebulae with the 21 μm Emission Feature

It has been more than 30 years since the enigmatic 21 μm emission feature was first discovered in protoplanetary nebulae (PPNs). Although dozens of different dust carrier candidates have been proposed, there is as yet no widely accepted one. We present the results of molecular observations toward 21 μm objects using the 10 m Submillimeter Telescope of Arizona Radio Observatory in the 1.3 mm band and the 13.7 m telescope of Purple Mountain Observatory in the 3 mm band, aiming to investigate whether the gas-phase environments of these unusual sources have some peculiarities compared to normal PPNs. We detect 31 emission lines belonging to seven different molecular species, most of which are the first detection in 21 μm PPNs. The observations provide clues to the identification of the 21 μm feature. We report a correlation study between the fractional abundance of gas-phase molecules and the strengths of the 21 μm emission. Our study shows that, given the small sample size, the 21 μm feature has weak or no correlations with the gas-phase molecules. Future radio observations of high spatial and spectral resolution toward a large sample are desirable to elucidate the 21 μm emission phenomena.

Free radical scavenging behaviour of the plant-beneficial secondary metabolite 2,4-diacetylphloroglucinol derivatives under physiological conditions: A joint experimental and theoretical study

Undoubtedly, natural products (NPs) offer a crucial foundation for crafting novel biologically relevant scaffolds. Among these, 2,4-diacetylphloroglucinol (DAPG) stands out as a polyketide compound produced by Pseudomonads spp, showcasing substantial antimicrobial activity. This study focuses on synthesising derivatives of DAPG and delving into their structural characteristics, tautomerism, and antiradical properties. Through density functional theory (DFT) calculations at the B3LYP/def2-SVP level, we examined the thermodynamic parameters governing the double H+/e−radical trapping processes. These investigations encompassed both gas phase and physiological environments (lipid-like and aqueous solution media). Comparative analyses were conducted with its analogue (2,4-diisobutyrylphloroglucinol, DBPG), its parent compound (phloroglucinol, PG), and a commercial antioxidant standard (2-butylated hydroxyanisole, 2-BHA). This study unveils that DAPG exhibits a preference for double-sequential proton loss electron transfer (dSPLET) as the favoured mechanism within physiological environments. Additionally, we computed redox potentials and equilibrium constants to discuss the effectiveness of the overall scavenging process against diverse reactive oxygen, nitrogen, and sulphur species (ROS, RNS, and RSS). Further insights were gained through molecular docking studies, evaluating the potential inhibition against several ROS-generating enzymes such as xanthine oxidase (XO), lipoxygenase (LO), CYP2C9 (CP450), and NADPH-oxidase (NO). Comprehensive discussions regarding the effects of modifications on PG rings were also conducted. In addition, bioinformatic POM (Petra/Osiris/Molinspiration) analyses were reported to aid in clarifying the experimental data and DFT calculations. Ultimately, this study advocates for the development of potent acyl phloroglucinols (ACPLs)-based antiradical agents, shedding light on how structural characteristics influence their radical scavenging potential.

Understanding Performance Limitations in Water Splitting Photoelectrodes at the Nanoscale

Photoelectrochemical (PEC) water splitting is a promising route for efficient conversion of solar energy into chemical fuels. In this context, economically viable photosystems are often based of semiconductor thin films which are polycrystalline or nanostructured with highly complex architectures e.g. with boundaries between differently orientated grains, different crystal facet orientations, as well as locally varying composition or phase. These nano- to micrometer properties often control critical processes, such as efficiency and stability, of the macroscale system. To understand the impact of nanoscale properties on the macroscopic performance, we aim at resolving local structural, chemical, and optoelectronic heterogeneities and at elucidating their effect on light-driven processes.In this work, we use a correlative approach to elucidate the nanoscale properties of polycrystalline BiVO4 thin films – a promising material for solar water splitting. Mapping of the local charge transport properties by photoconductive atomic force microscopy (pc-AFM) reveals the tolerance to grain boundaries.[1] Interestingly, scanning nearfield infrared microscopy shows strongly varying absorption from VO4 stretching modes between grains and at grain boundaries which correlate with the heterogeneities in the local photoconductivity across the polycrystalline thin films. Furthermore, local temperature-dependent current-voltage spectroscopy show that the low intrinsic bulk conductivity of BiVO4 limits the electron transport through the film, and that the transport mechanism can be attributed to space charge limited current (SCLC) in the presence of trap states.[1] Performing the same measurements in-situ in controlled gas-phase environment reveals the influence of chemical interactions of adsorbed oxygen and water on charge transport and interfacial charge transfer.[2] For BiVO4, we demonstrate that adsorbed oxygen acts as a surface trap state for electrons, which enhances the built-in potential and depletes the BiVO4 layer. Overall, combining insights from different nanoscale techniques generates a comprehensive picture of charge separation, transport, and transfer at the nanoscale. The gained nanoscale understanding of energy materials enables the rational design of durable and efficient solar fuel devices.[1] Eichhorn et al., Nat. Commun. 9, 2597(2018).[2] Eichhorn et al., ACS Appl. Mater. Interfaces, 10, 41, 35129 (2018).

Infrared Fingerprints of the CO2 Conversion into Methanol at Cu(s)/ZrO2(s): An Experimental and Theoretical Study

AbstractThe methanol economy is an attractive approach to tackle the current concerns over the depletion of natural resources and the global warming intrinsically associated with the use of fossil fuels. This can be achieved by hydrogenation of carbon dioxide to produce methanol, a liquid fuel with potential use in civil transportation. In this study, we aim to pinpoint the intermediates that are involved in the catalytic CO2 conversion into methanol on pure zirconia (ZrO2), Cu and Cu/ZrO2 systems. To accomplish this, we make use of infrared (IR) spectroscopy measurements and quantum chemical simulations within the hybrid density functional theory (DFT) framework. At 250 °C and p~30 bar, the main species formed on the partially hydroxylated ZrO2 is bidentate formate, whereas the co‐production of bicarbonate is relevant upon cooling to T=25 °C. On pure Cu, the IR fingerprints of methanol and carbon dioxide indicate their presence in the gas phase and surface environment, albeit formate/formic acid and methoxy species are also detected at these experimental conditions. The production of methanol on Cu/ZrO2 is mostly dependent on the Cu catalyst, but the higher amount of the methoxy intermediate can be correlated with the consumption of formate adsorbed on ZrO2 or at the Cu/ZrO2 interface. On the Cu/ZrO2 mixture, the reaction mechanism is likely to involve formate as the main intermediate, instead of CO which would result from the reverse water‐gas shift reaction. Ultimately, the higher activity shown by the Cu/ZrO2 mixture might be associated with the extra‐production of methoxy/methanol catalyzed by ZrO2 in the presence of Cu.

Synthesis, Spectroscopic Characterization, DFT, and Molecular Docking Analysis of Some Salicylideneaniline Schiff Base Derivatives as Potential Antioxidant Compounds

This study explores the synthesis and characterization of three Schiff base compounds, namely N-(2-hydroxybenzylidene)-m-chloroaniline (1), N-(2-hydroxybenzylidene)-m-nitroaniline (2), and N-(2-hydroxybenzylidene)-m-methoxyaniline (3). Comprehensive spectroscopic analyses involving FT-IR, H1NMR, and UV-Vis were employed to elucidate their molecular structures. Theoretical calculations were conducted using the DFT/B3LYP method with the 6-311 + G (d, p) basis set, elucidating electronic transitions and providing comprehensive vibrational assignments. The study identifies key electronic features of these compounds by analyzing global chemical reactivity descriptors. Density functional theory (DFT) was employed to assess the ability of these compounds to scavenge free radicals, both in the gas phase and solvent environment, focusing on three primary mechanisms: hydrogen atom transfer (HAT), stepwise electron-transfer-proton transfer (ET-PT), and sequential proton-loss-electron transfer (SPLET). Additionally, the research explores drug-likeness properties and conducts molecular docking investigations against the ubiquinol cytochrome c reductase protein (UQCRB) to gain further insights into potential biological activities.

Theoretical study on the potential environmental and ecological risk of 4-ethylphenol induced by hydroxyl radical

This study closely examines the environmental fate of 4-ethylphenol (4-EP), a significant byproduct of biomass combustion. We employed quantum chemical calculations to investigate the reaction mechanism, kinetics, and ecotoxicity of 4-EP initiated by OH radicals in various environments (aqueous, atmospheric liquid, atmospheric and inhomogeneous phases). Our findings highlight that solvent effects contribute to a higher OH-addition reaction branching ratio (Γadd) of 0.68 for 4-EP in an aqueous solution, compared to 0.26 in the gas-phase environment and 0.22 in the inhomogeneous environment at 298 K. We determined the rate constants for the liquid-phase, gas-phase, and nonhomogeneous phase to be 1.14 × 109 s−1 M−1, 3.09 × 109 s−1 M−1, and 6.19 × 1014 s−1 M−1, respectively. Notably, the adsorption of mineral particles considerably enhances the reaction rate of 4-EP with OH radicals. 4-ethylbenzene-1,2-diol, 4-hydroxycyclohexa-3,5-diene-1,2-dione, 1-ethyl-6-methyl-6H-benzo(c)chromene-4,9-diol, 5-ethyl-6'-(1-hydroxyethyl)-(1,1′-biphenyl)-2,3,3′-triol and 2-ethyl-4,6,9-trimethyl-6H-benzo(c) chromene are major products in both gas-phase and liquid-phase reactions, and (2Z, 4Z)-4-ethyl-6-oxohexa-2,4-dienoic acid is also one of the major products in gas-phase reactions. Toxicological predictions indicate that the ecotoxicity of 4-ethyl-6-methyl-6H-benzo(c)chromene-1,9-diol, 2-ethyl-6-methyl-6H-benzo(c)chromene-3,9-diol, and 2-ethyl-4,6,9-trimethyl-6H-benzo(c) chromene surpassed that of 4-EP. However, the toxicity of the reaction products is reduced in the presence of NOx. This investigation provides an exhaustive theoretical foundation for comprehending the degradation behavior of 4-EP and underscores the need to consider various environmental factors in assessing the potential risk of biomass combustion by products.

Direct Evidence of Dynamic Metal Support Interactions in Co/TiO2 Catalysts by Near-Ambient Pressure X-ray Photoelectron Spectroscopy.

The interaction between metal particles and the oxide support, the so-called metal-support interaction, plays a critical role in the performance of heterogenous catalysts. Probing the dynamic evolution of these interactions under reactive gas atmospheres is crucial to comprehending the structure-performance relationship and eventually designing new catalysts with enhanced properties. Cobalt supported on TiO2 (Co/TiO2) is an industrially relevant catalyst applied in Fischer-Tropsch synthesis. Although it is widely acknowledged that Co/TiO2 is restructured during the reaction process, little is known about the impact of the specific gas phase environment at the material's surface. The combination of soft and hard X-ray photoemission spectroscopies are used to investigate in situ Co particles supported on pure and NaBH4-modified TiO2 under H2, O2, and CO2:H2 gas atmospheres. The combination of soft and hard X-ray photoemission methods, which allows for simultaneous probing of the chemical composition of surface and subsurface layers, is one of the study's unique features. It is shown that under H2, cobalt particles are encapsulated below a stoichiometric TiO2 layer. This arrangement is preserved under CO2 hydrogenation conditions (i.e., CO2:H2), but changes rapidly upon exposure to O2. The pretreatment of the TiO2 support with NaBH4 affects the surface mobility and prevents TiO2 spillover onto Co particles.

The Value of Different Experimental Observables: A Transient Absorption Study of the Ultraviolet Excitation Dynamics Operating in Nitrobenzene.

Excess energy redistribution dynamics operating in nitrobenzene under hexane and isopropanol solvation were investigated using ultrafast transient absorption spectroscopy (TAS) with a 267 nm pump and a 340-750 nm white light continuum probe. The use of a nonpolar hexane solvent provides a proxy to the gas-phase environment, and the findings are directly compared with a recent time-resolved photoelectron imaging (TRPEI) study on nitrobenzene using the same excitation wavelength [L. Saalbach et al., J. Phys. Chem. A 2021, 125, 7174-7184]. Of note is the observation of a 1/e lifetime of 3.5-6.7 ps in the TAS data that was absent in the TRPEI measurements. This is interpreted as a dynamical signature of the T2 state in nitrobenzene─analogous to observations in the related nitronaphthalene system, and additionally supported by previous quantum chemistry calculations. The discrepancy between the TAS and TRPEI measurements is discussed, with the overall findings providing an example of how different spectroscopic techniques can exhibit varying sensitivity to specific steps along the overall reaction coordinate connecting reactants to photoproducts.

Surface evolution of Pt/MoO3/4H-SiC(0001) investigated by in situ near-ambient pressure X-ray photoelectron spectroscopy

Achieving effective Ohmic contact between SiC and metal electrodes remains a challenge due to the high Schottky barrier resulting from the large mismatch between the deep-lying valence band of SiC and Fermi level of metals. One promising approach to address this issue is to introduce a high-work-function interfacial layer between the metal and semiconductor. However, the interaction mechanisms of the inserted high-work-function interfacial layer between metal electrodes and the SiC substrate have been rarely studied systematically. In this work, layers of high-work-function molybdenum trioxide (MoO3) and platinum (Pt) were successively grown on the 4H-SiC(0001) surface via conventional physical vapour deposition (PVD). We investigated the chemical and electronic structure evolutions upon Pt deposition on MoO3/4H-SiC(0001) using in situ near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and ultraviolet photoelectron spectroscopy (UPS). Subsequently, the evolutions of Pt/MoO3/4H-SiC(0001) system during annealing under ultra-high vacuum (UHV) or various gas phase environments (H2 and O2) were studied via in situ NAP-XPS and UPS. Our results reveal that Pt showed its thermal stability during the annealing process, while Mo presented its versatile chemical characteristics. These results depict a detailed chemical feature of the Pt/MoO3/4H-SiC(0001) system and help gain a better understanding about the impact of different environments on Pt/MoO3 interface.

Structural studies of supramolecular complexes and assemblies by ion mobility mass spectrometry.

Recent advances in instrumentation and development of computational strategies for ion mobility mass spectrometry (IM-MS) studies have contributed to an extensive growth in the application of this analytical technique to comprehensive structural description of supramolecular systems. Apart from the benefits of IM-MS for interrogation of intrinsic properties of noncovalent aggregates in the experimental gas-phase environment, its merits for the description of native structural aspects, under the premises of having maintained the noncovalent interactions innate upon the ionization process, have attracted even more attention and gained increasing interest in the scientific community. Thus, various types of supramolecular complexes and assemblies relevant for biological, medical, material, and environmental sciences have been characterized so far by IM-MS supported by computational chemistry. This review covers the state-of-the-art in this field and discusses experimental methods and accompanying computational approaches for assessing the reliable three-dimensional structural elucidation of supramolecular complexes and assemblies by IM-MS.

Core-Level Photoelectron Angular Distributions at the Liquid-Vapor Interface.

ConspectusPhotoelectron spectroscopy (PES) is a powerful tool for the investigation of liquid-vapor interfaces, with applications in many fields from environmental chemistry to fundamental physics. Among the aspects that have been addressed with PES is the question of how molecules and ions arrange and distribute themselves within the interface, that is, the first few nanometers into solution. This information is of crucial importance, for instance, for atmospheric chemistry, to determine which species are exposed in what concentration to the gas-phase environment. Other topics of interest include the surface propensity of surfactants, their tendency for orientation and self-assembly, as well as ion double layers beneath the liquid-vapor interface. The chemical specificity and surface sensitivity of PES make it in principle well suited for this endeavor. Ideally, one would want to access complete atomic-density distributions along the surface normal, which, however, is difficult to achieve experimentally for reasons to be outlined in this Account. A major complication is the lack of accurate information on electron transport and scattering properties, especially in the kinetic-energy regime below 100 eV, a pre-requisite to retrieving the depth information contained in photoelectron signals.In this Account, we discuss the measurement of the photoelectron angular distributions (PADs) as a way to obtain depth information. Photoelectrons scatter with a certain probability when moving through the bulk liquid before being expelled into a vacuum. Elastic scattering changes the electron direction without a change in the electron kinetic energy, in contrast to inelastic scattering. Random elastic-scattering events usually lead to a reduction of the measured anisotropy as compared to the initial, that is, nascent PAD. This effect that would be considered parasitic when attempting to retrieve information on photoionization dynamics from nascent liquid-phase PADs can be turned into a powerful tool to access information on elastic scattering, and hence probing depth, by measuring core-level PADs. Core-level PADs are relatively unaffected by effects other than elastic scattering, such as orbital character changes due to solvation. By comparing a molecule's gas-phase angular anisotropy, assumed to represent the nascent PAD, with its liquid-phase anisotropy, one can estimate the magnitude of elastic versus inelastic scattering experienced by photoelectrons on their way to the surface from the site at which they were generated. Scattering events increase with increasing depth into solution, and thus it is possible to correlate the observed reduction in angular anisotropy with the depth below the surface along the surface normal.We will showcase this approach for a few examples. In particular, our recent works on surfactant molecules demonstrated that one can indeed probe atomic distances within these molecules with a high sensitivity of ∼1 Å resolution along the surface normal. We were also able to show that the anisotropy reduction scales linearly with the distance along the surface normal within certain limits. The limits and prospects of this technique are discussed at the end, with a focus on possible future applications, including depth profiling at solid-vapor interfaces.