Binding energy | EPFL Graph Search

In physics and chemistry, binding energy is the smallest amount of energy required to remove a particle from a system of particles or to disassemble a system of particles into individual parts. In the former meaning the term is predominantly used in condensed matter physics, atomic physics, and chemistry, whereas in nuclear physics the term separation energy is used. A bound system is typically at a lower energy level than its unbound constituents. According to relativity theory, a ΔE decrease in the total energy of a system is accompanied by a decrease Δm in the total mass, where Δmc2 = ΔE. Types of binding energy There are several types of binding energy, each operating over a different distance and energy scale. The smaller the size of a bound system, the higher its associated binding energy. Mass–energy relation Mass–energy equivalence and Mass in special relativity A bound system is typically at a lower energy level than its unbound constituents because it

Interface Investigations on Titanium Nitride Bilayer Systems

Dominik Anwar Jaeger

Nanocomposite coatings composed of two phases with atomically sharp phase boundaries, show interesting mechanical properties. These properties are often originating from their high interface to volume ratio. Composites of nanocrystalline titanium nitride (TiN) grains surrounded by a one to two monolayer thick interlayer of silicon nitride (Si3N4) show an enhanced nanohardness. The central theme of this thesis is concernedwith the interfacial properties of two-dimensional bilayer systems, which are used as model systems to describe the interfaces occurring in nanocomposite coatings. The systems under investigation are TiN interfaces in contact with silicon (Si), silicon nitride (Si3N4) and aluminum nitride (AlN). The primary tool used to analyze the interfaces of bilayer systems is X-ray Photoelectron Spectroscopy (XPS) with emphasis put on the shake-up feature of the Ti 2p photoelectron line. Shake-ups in TiN are observed as an additional peak on the lower binding energy side of the energy lines of the Ti 2p orbitals. Shake-ups are strongly influenced by valence electrons and electron density distributions. This makes them a powerful tool to probe the chemical and electronic structure of TiN interfaces. The aim of this study is to utilize the shake-up energy and its intensity to gain insight into interfacial structures and correlate their changes to interfacial polarization and macroscopic mechanical properties. Single crystalline (sc-) and oxygen-free TiN as well as oxygen-free bilayer systems were deposited by unbalanced magnetron sputtering and analyzed by Angle Resolved (AR-)XPS. Bilayer samples were deposited and their quality was controlled using X-ray diffraction (crystallinity), Rutherford back scattering (elemental composition), and atomic force microscopy (roughness). All XPS samples were fabricated, transfered and analyzed whilst maintaining ultra high vacuum. A precise and self-consistent XPS data processing method was developed to evaluate Ti 2p spectra. This method accounts for the correct photoelectron line shape, background subtraction and photoelectron peak area intensity. Binding energy, shake-up energy and intensity ratios of shake-ups taken frompristine TiN surfaces are precisely determined, and the influence of oxygen on the information content in peak positions and intensities was investigated. The shake-up energy and intensity of bulk sc-TiN and its origin of the shake-up are discussed. An analytical description for the XPS signal ratio of bilayer systems is derived to separate the interfacial signals from the bulk information. The results obtained by this analytical description are strongly influenced by the interface thickness that has been found to be proportional to the overlayer thickness. The revealed interface properties show a correlation between the shake-up intensity and the interface morphology, oxygen content, overlayer material and overlayer thickness. AR-XPS and X-ray Photoelectron Diffraction (XPD) results were used to interpret the crystalline structure of the different TiN/AlN and TiN/Si3N4 bilayer systems. AlN shows XPD patterns indicating a crystalline growth of AlN on sc-TiN. The electrically insulating AlN overlayer creates a charge accumulation at the TiN interface, which results in an enhanced shake-up intensity. XPD patterns of Si3N4 systems revealed a crystalline growth of Si3N4 in the first 0.6nm. The intensity of the diffraction patterns reduces with increasing Si3N4 overlayer thickness due to a change in the growth behavior from crystalline to amorphous structures. Si3N4 films show, in comparison to AlN, reduced interface charging and hence a lower shakeup intensity. The crystalline growth of Si3N4 in the initial stages is hindered in systems where a bias voltage is applied to the substrate during the deposition process. In contrast to the unbiased systems, which have crystalline interfacial structures, the biased systems no longer show XPD patterns due to a loss of crystallinity. Additionally the shake-up intensity of biased systems is thickness-independent, which is in contrast to unbiased systems. The difference in the shake-up intensity of biased and unbiased Si3N4 is explained by a different band gap of the Si3N4 structure in the first two monolayers. This thesis shows that the increase in the shake-up intensity is correlated to intrinsic and extrinsic interface charging. The obtained results, in combination with theoretical structure models from literature, show that in one to two monolayer thick interlayers a build-up of interface polarization is unlikely. The observed nanohardness enhancement in TiN/Si3N4 systems is explained with already known hardness effects.

EPFL2012

A Cation Concentration Gradient Approach to Tune the Selectivity and Activity of CO2 Electroreduction

Xile Hu, Wenhao Ren

The linear scaling relationship of the binding energies of different intermediates limits the catalyst performance in CO 2 electroreduction. Here we demonstrate a cation concentration gradient strategy to promote the activity and tune the selectivity of CO 2 electroreduction, thereby breaking the scaling relationship. In optimal concentrations of the potassium acetate (KAc) electrolyte, Cu, Ag and In catalysts deliver current densities that are 7.1, 3.2, 2.7 times higher than those obtained in 0.5 M KAc for C 2 H 4 , CO, and formate production, respectively. Increasing the concentration of KAc also changes the selectivity from CO to formate on Ag, and from CO to C 2 products on Cu. In situ surface-enhanced Raman spectroscopy and computational simulations reveal that the binding energies of intermediates are changed at different electrolyte concentrations, which is due to a local electrostatic interaction modulated by potassium cations at the electrode surface.

2022

On the role of water density fluctuations in the inhibition of a proton channel

Lucie Monique Françoise Delemotte

Hv1 is a transmembrane four-helix bundle that transports protons in a voltage-controlled manner. Its crucial role in many pathological conditions, including cancer and ischemic brain damage, makes Hv1 a promising drug target. Starting from the recently solved crystal structure of Hv1, we used structural modeling and molecular dynamics simulations to characterize the channel's most relevant conformations along the activation cycle. We then performed computational docking of known Hv1 inhibitors, 2-guanidinobenzimidazole (2GBI) and analogs. Although salt-bridge patterns and electrostatic potential profiles are well-defined and distinctive features of activated versus nonactivated states, the water distribution along the channel lumen is dynamic and reflects a conformational heterogeneity inherent to each state. In fact, pore waters assemble into intermittent hydrogen-bonded clusters that are replaced by the inhibitor moieties upon ligand binding. The entropic gain resulting from releasing these conformationally restrained waters to the bulk solvent is likely a major contributor to the binding free energy. Accordingly, we mapped the water density fluctuations inside the pore of the channel and identified the regions of maximum fluctuation within putative binding sites. Two sites appear as outstanding: One is the already known binding pocket of 2GBI, which is accessible to ligands from the intracellular side; the other is a site located at the exit of the proton permeation pathway. Our analysis of the waters confined in the hydrophobic cavities of Hv1 suggests a general strategy for drug discovery that can be applied to any ion channel.

Natl Acad Sciences2016

Interface Investigations on Titanium Nitride Bilayer Systems

Dominik Anwar Jaeger

EPFL2012