The Theoretical Study of Interaction of Water Chloride Containing Environment Components with CuAl<Subscript>2</Subscript> Intermetallic Surface

DFT method in a cluster approximation has been used to simulate surfaces of intermetallics CuAl₂ as a structural part of aluminum copper alloys AA2XXX. Geometry and electronic structure of clusters at the surfaces (100) and (110) were calculated. Parameters of adsorbate (water molecules and chloride ions) interaction with the surfaces of the metals were calculated in details. It has been shown that water molecules prefer to adsorb at the intermetallic surface by oxygen atoms in atop sites. The influence of corrosive active chloride ions on the intermetallic surface destruction has been studied in the environment of water molecules for an original molecular model. It gave the possibility of the prevailing dissolution of the (110) surface as compared with the (100) surface. It has been shown that the intermetallic phase is a complicated electrochemical system with the regions of different crystallographic orientation and adsorption sites for the system aluminum–copper, which serve as active local cathode–anode regions. The presence of such regions initiates the intermetallic phase fracture.     

Molecular simulation of water behaviors on crystal faces of hydroxyapatite

The water behavior on (001) and (100) crystal faces of hydroxyapatite (HAP) were studied using molecular dynamics (MD) simulations. The study showed that the water molecules between the HAP faces were under conditions of strong electrical field and high pressure, and hence formed 2–3 well-organized water layers on the crystal surfaces. These structured water layers had ice-like features. Compared with the crystallographic [100] direction of HAP, the polarity along the [001] direction was stronger, which resulted in more structured water layers on the surface. The interaction of water molecules with the calcium and phosphate sites at the HAP-water interface was also studied. The results indicated the multiple pathways of water adsorption onto the HAP surfaces. This study revealed the formation and the detailed structure of water layers on HAP surfaces and suggested that the interfacial water played an important role in stabilizing the HAP particles in aqueous solutions. Translated from Chinese Journal of Inorganic Chemistry, 2006, 22(8): 1392–1400 (in Chinese)     

Adsorption‐induced changes of intramolecular optical transitions: PTCDA/NaCl and PTCDA/KCl

Structural and optical properties of isolated perylene‐3,4,9,10‐tetracarboxylic acid dianhydride molecules adsorbed on (100) oriented NaCl and KCl surfaces were studied theoretically to analyze the recently observed red‐shift of the optical excitation spectrum after adsorption (Müller et al., Phys. Rev. B, 2011, 83, 241203; Paulheim et al. Phys. Chem. Chem. Phys., 2013, 15, 4906). The ground‐state structures were obtained by periodic dispersion‐corrected density functional theory (DFT) calculations. For the excited‐state calculations, nonperiodic time‐dependent DFT methods were applied for a cluster model embedded in point charges. The range‐separated hybrid functional CAM‐B3LYP was used. Correlation‐consistent basis sets were used and the calculated excitation energies were extrapolated to the complete basis set limit. The shift of the first optical excitation energy was analyzed in terms of electronic and geometric contributions. It was found that both the distortion of the molecule due to the interaction with the surface and the electrostatic potential of the surface play an important role. © 2015 Wiley Periodicals, Inc.     

Molecular dynamic study of electric potentials in water clusters containing the sodium or chlorine atom

Molecular dynamics with design is used to calculate the electric potentials of isolated water clusters containing Na⁺ or Cl⁻. The number of water molecules in the clusters is from 4 to 14. It is noted that electrostatic interaction plays a dominant role in the clusters; the dependence of the dielectric constant of the cluster on the size of the latter is determined. Institute of Thermal Physics, Ural Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 1, pp. 66–73, January–February, 1998.     

Microsolvation of DMSO: Density functional study on the structure and polaraizabilities

The structure and stability for the association of water with dimethyl sulfoxide (DMSO) are investigated using the density functional M06‐2X level theory. Stable complexes are formed by the formation of hydrogen bonding between water and oxygen atom of DMSO molecule, while the electrostatic force between water and DMSO plays a vital role in deciding the structure. The water‐DMSO interactions are stronger than the interwater hydrogen bonds, which can be inferred from the shorter DMSO‐water bond distance compared with the water–water bond distance. The calculated solvent association energy does not saturate, and it remains favorable to attach additional water molecules to the existing water network. The calculated IR spectra shifts supports the formation stronger hydrogen bonding, while the electrostatic potential (ESP) plot supports the existence of weaker electrostatic interaction in the studied clusters. The polarizabilities for the ground state clusters were found to increase monotonically with the cluster size. The presence of additional electrostatic bonding between water and DMSO, devastates the linear hydrogen‐bonding network. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Molecular dynamics simulation study of water adsorption on hydroxylated graphite surfaces

In this paper, we present results from molecular dynamic simulations devoted to the characterization of the interaction between water molecules and hydroxylated graphite surfaces considered as models for surfaces of soot emitted by aircraft. The hydroxylated graphite surfaces are modeled by anchoring several OH groups on an infinite graphite plane. The molecular dynamics simulations are based on a classical potential issued from quantum chemical calculations. They are performed at three temperatures (100, 200, and 250 K) to provide a view of the structure and dynamics of water clusters on the model soot surface. These simulations show that the water-OH sites interaction is quite weak compared to the water-water interaction. This leads to the clustering of the water molecules above the surface, and the corresponding water aggregate can only be trapped by the OH sites when the temperature is sufficiently low, or when the density of OH sites is sufficiently high.     

Water on extended and point defects at MgO surfaces

The interaction of water with extended defects such as mono- and diatomic steps at the MgO(100) surface is investigated through first-principles simulations, as a function of water coverage. At variance with flat MgO(100) terraces, water adsorption is always dissociative on mono- and diatomic steps, as well as on MgO(110) surfaces. In most of the equilibrium configurations, the oxygen of the hydroxyl groups is two- or fourfold coordinated, but single-coordinated OH groups can be stabilized at diatomic step edges. The structural properties of the hydroxyl groups are discussed as a function of their coordination numbers and mutual interactions, as well as the surface defect morphology. It is shown that characteristics of water adsorption are primarily driven by the coordination number of the surface acid-base pair where the dissociation occurs. However, the OH groups resulting from water dissociation are also considerably stabilized by the electrostatic interaction with coadsorbed protons. At low coverage such an interaction, considerably stronger than hydrogen bonding, practically hinders any proton diffusion away from its neighboring hydroxyl. The computed adsorption energies allow us to discuss the onset of water desorption from flat MgO(100) terraces, diatomic and monoatomic steps, and from Mg-O divacancy.     

Vibrational Spectroscopy As a Probe of Surface Heterogeneity: CO on NaCl(100)

The fundamental (Δv = 1 ← 0) and the first overtone (Δv = 2 ← 0) transitions of monolayer physisorbed CO on NaCl(100) single crystal surfaces at 5 K have been investigated using polarized Fourier transform infrared spectroscopy. Comparisons of the transition frequencies, bandwidths and absorbances for these two transitions together with those of dilute isotopes allow us to isolate the contribution of dynamic and static coupling effects of molecules within the monolayer. Homogeneous and heterogeneous effects can also be distinguished from band profiles of these various transitions. We conclude that the residual line broadening of 0.1 cm^?1 at 5 K for the isolated CO isotopes arises from heterogeneous surface effects. We set an upper limit of 0.07 cm^?1 for the linewidth of single CO molecules on NaCl(lOO) due to surface heterogeneity. A lower limit of × 10^?8 cm^?1 is provided by the vibrational lifetime of adsorbed CO molecules. Sharpness of the vibrational features shows that infrared spectroscopy of adsorbate is a sensitive method for probing surface and adlayer irregularities of adsorbed molecules on a single crystal.     

Comparison of cation adsorption by isostructural rutile and cassiterite

Macroscopic net proton charging curves for powdered rutile and cassiterite specimens with the (110) crystal face predominant, as a function of pH in RbCl and NaCl solutions, trace SrCl(2) in NaCl, and trace ZnCl(2) in NaCl and Na Triflate solutions, are compared to corresponding molecular-level information obtained from static DFT optimizations and classical MD simulations, as well as synchrotron X-ray methods. The similarities and differences in the macroscopic charging behavior of rutile and cassiterite largely reflect the cation binding modes observed at the molecular level. Cation adsorption is primarily inner-sphere on both isostructural (110) surfaces, despite predictions that outer-sphere binding should predominate on low bulk dielectric constant oxides such as cassiterite (ε(bulk) ≈ 11). Inner-sphere adsorption is also significant for Rb(+) and Na(+) on neutral surfaces, whereas Cl(-) binding is predominately outer-sphere. As negative surface charge increases, relatively more Rb(+), Na(+), and especially Sr(2+) are bound in highly desolvated tetradentate fashion on the rutile (110) surface, largely accounting for enhanced negative charge development relative to cassiterite. Charging curves in the presence of Zn(2+) are very steep but similar for both oxides, reflective of Zn(2+) hydrolysis (and accompanying proton release) during the adsorption process, and the similar binding modes for ZnOH(+) on both surfaces. These results suggest that differences in cation adsorption between high and low bulk dielectric constant oxides are more subtly related to the relative degree of cation desolvation accompanying inner-sphere binding (i.e., more tetradentate binding on rutile), rather than distinct inner- and outer-sphere adsorption modes. Cation desolvation may be favored at the rutile (110) surface in part because inner-sphere water molecules are bound further from and less tightly than on the cassiterite (110) surface. Hence, their removal upon inner-sphere cation binding is relatively more favorable.     

Electrochemical attachment of motile bacterial cells to gold

Selective attachment of Escherichia coli K-12 bacterial cells to charged gold surfaces was demonstrated. Electrostatic binding of E. coli K-12 bacterial cells to positively charged surfaces was observed starting at +750 mV. The binding of E. coli K-12 cells to positively charged gold surfaces is proposed to occur due to long-range electrostatic interactions between the negatively charged O-chain of lipopolysaccharide (LPS) molecules protruding the bacterial cell body and the electrode surface. Removing LPS alters the cellular surface charge and results in cellular attachment to negatively charged surfaces. Thus, applying an electrical potential allows for the direct, real time detection of live, dead or damaged bacterial cells. The attachment of E. coli K-12 bacterial cells to surfaces with an applied potential substantiates the hypothesis that an electrostatic interaction is responsible for the binding of bacterial cells to positively charged molecular assemblies on surfaces used for building bacterial microarrays.