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Potential pulse perturbation time-resolved scanning tunneling microscopy is used to investigate the growth and dissolution dynamics of nanoscale islands. It is concluded that the properties of the islands can be controlled by tailoring the potential pulse perturbation.

Research was conducted to examine quantitative polarity scales based on second harmonic spectroscopy. The polarity of various liquid/liquid and vapor/liquid interfaces was determined following the demonstration that second harmonic spectroscopy can be utilized in the measurement of interface polarity. Results indicate the possible dominance of the long-range solute-solvent interactions in determining the difference in the excited- and ground-state solvation energies of the interface adsorbed molecules.

We report an investigation of charge transfer in high-k dielectric stacks on Si by second harmonic generation (SHG). Ultrathin (2–6 nm) films of HfO2, ZrO2, and Al2O3 grown on Si surfaces by atomic layer deposition were investigated and compared to conventional SiO2-based gate dielectrics. From the SHG rotational anisotropy (SHG-RA) of Si-(high-k) and Si–SiO2 systems, optical roughness of the films was found to increase in the following order: SiO2, Al2O3, and (ZrO2 and HfO2). The optical roughness is regarded as a quantity describing the nonuniformity in the distribution of interfacial defects capable of charge trapping. Time dependent second harmonic generation (TD-SHG) measurements were carried out to understand charge trapping and detrapping dynamics and trapped charge densities. Relative comparison of the four dielectrics revealed that Al2O3 films have the highest densities of trapped and fixed charge while silicon oxides exhibited less charge trapping, consistent with electrical measurements performed on similar structures. In contrast to SiO2 films, detrapping was significantly suppressed in the high-k films due to significantly reduced leakage currents. We also observed ambient effects in charge trapping at the dielectric/air(vacuum) interface that could be significantly reduced by covering the dielectric film with a thin (semitransparent) metal (aluminum) overlayer. [ABSTRACT FROM AUTHOR]

The oxidation of H terminated silicon surfaces is a significant and controversial problem in silicon device fabrication. Second-harmonic generation rotational anisotropy (SHG–RA) provides a convenient means to monitor the chemical state of the Si surfaces, and to follow the conversion of H terminated surface to SiO2 by oxidation as a function of time in ambient. The change in SHG–RA of Si(111)–H was shown to correlate well with the ellipsometric thickness. SHG is sensitive to the initial stage of oxidation (induction period) as well as to the logarithmic oxide growth. SHG is sensitive to the electronic properties of the surface, therefore it is a sensitive probe of the quality of H terminated Si(111) surface. Under ambient conditions, (20% relative humidity, 23 °C) the initial oxidation rate is at most 2×10-6 ML/s. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Infrared second harmonic generation (IR-SHG) spectroscopy, an extension of spectroscopic SHG to the IR, is described and applied to the investigation of germanium-dielectric interfaces in the spectral region near the direct and indirect band gap of the bulk semiconductor. The spectrum of the Ge[SUB111] - GeO[SUB2] interface, in the 1100-2000 nm fundamental wavelength range, is dominated by a resonance at 590 nm. This feature is assigned to the direct Λ[SUB25]7gt;Λ[SSUB2] transition between valence and)conduction band states. Polarization and azimuth dependent IR-SHG spectroscopy revealed that the anisotropic contribution, containing bulk quadrupole, ξ, and surface, δ[SUB1], nonlinear susceptibility terms, dominates the 590 nm resonance. S-termination of Ge(111) significantly modifies the interface nonlinear optical response. The IR-SHG spectrum of S-Ge(111) presents a new, possibly surface resonance at ∼565 nm, in addition to the resonance inherent to the bulk Ge at 590 nm, tentatively assigned to an interband transition of Ge atoms associated with the surface. [ABSTRACT FROM AUTHOR]

The oxidation of Si (111)-H surface by second-harmonic generation rotational anisotropy (SHG-RA) at 800 nm is investigated. It is shown that 800 nm SHG is sensitive to the electronic properties of the interface and could be used to probe the evolution of the chemical state of Si surface.

Focuses on the role of chemical and morphological heterogeneities of carbon sorbents in gas phase adsorption. Investigation on the effects of chemical and morphological heterogeneities on mercury adsorption; Occurrence of plasma oxidation in physisorption; Comparison of adsorption and desorption in gas phase elemental mercury.

Solid-water interfaces are crucial for clean water, conventional and renewable energy, and effective nuclear waste management. However, reflecting the complexity of reactive interfaces in continuum-scale models is a challenge, leading to oversimplified representations that often fail to predict real-world behavior. This is because these models use fixed parameters derived by averaging across a wide physicochemical range observed at the molecular scale. Recent studies have revealed the stochastic nature of molecular-level surface sites that define a variety of reaction mechanisms, rates, and products even across a single surface. To bridge the molecular knowledge and predictive continuum-scale models, we propose to represent surface properties with probability distributions rather than with discrete constant values derived by averaging across a heterogeneous surface. This conceptual shift in continuum-scale modeling requires exponentially rising computational power. By incorporating our molecular-scale understanding of solid-water interfaces into continuum-scale models we can pave the way for next generation critical technologies and novel environmental solutions., (© 2024. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

A previous combined experimental and theoretical study found that the position of anchoring groups on a phenanthrene (PHE) backbone played a large role in determining the single-molecule conductance of the PHE derivative. However, a consistent 0.1 G 0 feature was found across all PHE derivatives. To understand this, the previously investigated PHE derivatives were placed flat on a simulated Au substrate with a scanning tunneling microscope (STM) tip over PHE and conductance was calculated using the non-equilibrium Green's function technique in conjunction with density functional theory (NEGF-DFT). The location of the tip was varied to find the most conductive and most energetically favorable arrangements, which did not coincide. Furthermore, the variation in conductance found in erect junctions was not present when PHE derivatives were lying flat, with all derivatives calculated to have conductance values around 0.1 G 0 ., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

The molecular details of an electrocatalytic interface play an essential role in the production of sustainable fuels and value-added chemicals. Many electrochemical reactions exhibit strong cation-dependent activities, but how cations affect reaction kinetics is still elusive. We report the effect of cations (K + , Li + , and Ba 2+ ) on the interfacial water structure using second-harmonic generation (SHG) and classical molecular dynamics (MD) simulation. The second- (χ H 2 O (2) ) and third-order (χ H 2 O (3) , suggesting that cations can affect the interfacial water orientation. MD simulation reproduces experimental SHG observations and further shows that the competition between cation hydration and interfacial water alignment governs the net water orientation. The impact of cations on interfacial water supports a cation hydration-mediated mechanism for hydrogen electrocatalysis; i.e., the reaction occurs via water dissociation followed by cation-assisted hydroxide/water exchange on Pt. Our study highlights the role of interfacial water in electrocatalysis and how innocent additives (such as cations) can affect the local electrochemical environment.2+ compared to those of K + , suggesting that cations can affect the interfacial water orientation. MD simulation reproduces experimental SHG observations and further shows that the competition between cation hydration and interfacial water alignment governs the net water orientation. The impact of cations on interfacial water supports a cation hydration-mediated mechanism for hydrogen electrocatalysis; i.e., the reaction occurs via water dissociation followed by cation-assisted hydroxide/water exchange on Pt. Our study highlights the role of interfacial water in electrocatalysis and how innocent additives (such as cations) can affect the local electrochemical environment.

The utility of UiO-67 Metal-Organic Frameworks (MOFs) for practical applications requires a comprehensive understanding of intermolecular host-guest MOF-analyte interactions. To investigate intermolecular interactions between UiO-67 MOFs and complex molecules, it is useful to evaluate the interactions with simple polar and non-polar analytes. This problem is approached by investigating the interactions of polar (acetone and isopropanol) and non-polar (n-heptane) molecules with functionalized UiO-67 MOFs via temperature programmed desorption mass spectrometry and temperature programmed Fourier transform infrared spectroscopy. We find that isopropanol, acetone, and n-heptane bind reversibly and non-destructively to UiO-67 MOFs, where MOF and analyte functionality influence relative binding strengths (n-heptane ≈ isopropanol > acetone). During heating, all three analytes diffuse into the internal pore environment and directly interact with the μ3-OH groups located within the tetrahedral pores, evidenced by the IR response of ν(μ3-OH). We observe nonlinear changes in the infrared cross sections of the ν(CH) modes of acetone, isopropanol, and n-heptane following diffusion into UiO-67. Similarly, acetone's ν(C=O) infrared cross section increases dramatically when diffused into UiO-67. Ultimately, this in situ investigation provides insights into how individual molecular functional groups interact with UiO MOFs and enables a foundation where MOF interactions with complex molecular systems can be evaluated., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The modulation of charge transport through single molecules can be established by using the intrinsic characteristics of molecules and the physical properties of their environment. Therefore, the impact of the solvent on the electronic properties of molecules in the junction and their charge transport behavior are of great interest. Here, for the first time, we focused on charge transport through dimethylaminobenzonitrile (DMABN). This molecule shows unique behavior, specifically noticeable electronic structure modulations in bulk solvents, e.g., dual fluorescence in a polar environment. Using the scanning tunneling microscopy break junction (STM-BJ) technique, we find an order of magnitude increase in conductance along with a second conductance value in polar solvents over nonpolar solvents. Inspired by the twisted intramolecular charge transfer (TICT) explanation of the famous dual fluorescence of DMABN in polar solvents, we hypothesize stabilization of twisted DMABN molecules in the junction in more polar solvents. Ab initio molecular dynamics (AIMD) simulations using density functional theory (DFT) show that DMABN can twist in the junction and have a larger dipole moment compared to planar DMABN junction geometries, supporting the hypothesis. The nonequilibrium Green's function with the DFT approach (NEGF-DFT) is used to calculate the conductance throughout the AIMD trajectory, finding a significant change in the frontier orbitals and transmission function at large internal twisting angles, which can explain the dual conductance in polar solvents in STM-BJ experiments.

A composite of catalytic Lewis acidic zirconium oxyhydroxides (8 wt %) and a covalent organic framework (COF) was synthesized. X-ray diffraction and infrared (IR) spectroscopy reveal that COF's structure is preserved after loading with zirconium oxyhydroxides. Electron microscopy confirms a homogeneous distribution of nano- to sub-micron-sized zirconium clusters in the COF. 3D X-ray tomography captures the micron-sized channels connecting the well-dispersed zirconium clusters on the COF. The crystalline ZrO x (OH) y @COF's nanostructure was model-optimized via simulated annealing methods. Using 0.8 mol % of the catalyst yielded a turnover number of 100-120 and a turnover frequency of 160-360 h -1 for Knoevenagel condensation in aqueous medium. Additionally, 2.2 mol % of catalyst catalyzes the hydrolysis of dimethyl nitrophenyl phosphate, a simulant of nerve agent Soman, with a conversion rate of 37% in 180 min. The hydrolytic detoxification of the live agent Soman is also achieved. Our study unveils COF-stabilized ZrO x (OH) y as a new class of zirconium-based Lewis + Bronsted-acid catalysts., Competing Interests: The authors declare no competing interests., (© 2023 The Author(s).)

Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by "anomalies" or "non-idealities" such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide- and silicate-water interfaces. This critical review discusses how science progresses from understanding ideal solid-water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. We anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.

Hypothesis: Understanding the microscopic driving force of water wetting is challenging and important for design of materials. The relations between structure, dynamics and hydrogen bonds of interfacial water can be investigated using molecular dynamics simulations., Experiments and Simulations: Contact angles at the alumina (0001) and (112‾0) surfaces are studied using both classical molecular dynamics simulations and experiments. To test the superhydrophilicity, the free energy cost of removing waters near the interfaces are calculated using the density fluctuations method. The strength of hydrogen bonds is determined by their lifetime and geometry., Findings: Both surfaces are superhydrophilic and the (0001) surface is more hydrophilic. Interactions between surfaces and interfacial waters promote a templating effect whereby the latter are aligned in a pattern that follows the underlying lattice of the surfaces. Translational and rotational dynamics of interfacial water molecules are slower than in bulk water. Hydrogen bonds between water and both surfaces are asymmetric, water-to-aluminol ones are stronger than aluminol-to-water ones. Molecular dynamics simulations eliminate the impacts of surface contamination when measuring contact angles and the results reveal the microscopic origin of the macroscopic superhydrophilicity of alumina surfaces: strong water-to-aluminol hydrogen bonds., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Inc.)