Shah Haider Khan

Dynamic Solidification in Nanoconfined Water Films

Mechanical properties of nanoconfined water layers are still poorly understood and continue to create controversy, despite their importance for biology and nanotechnology. We report on dynamic nanomechanical measurements of water films compressed to a few single molecular layers. We show that the mechanical properties of nanoconfined water layers change significantly with their dynamic state. In particular, we observed a sharp transition from viscous to elastic response even at extremely slow compression rates, indicating that mechanical relaxation times increase dramatically once water is compressed to less than 3-4 molecular layers.

Ab Initio Investigation of the Structural, Electronic and Optical Properties of the Li2In2XY6 (X = Si, Ge; Y = S, Se) Compounds

The structural, electronic and optical properties of the Li2In2XY6 (Xxa0=xa0Si, Ge; Yxa0=xa0S, Se) compounds, which are scarcely studied by theoretical methods previously, have been investigated by ab initio calculations based on the density functional theory (DFT) in this article by using the full potential linearized augmented plane wave method. The equilibrium structural ground state properties of the Li2In2XY6 (Xxa0=xa0Si, Ge; Yxa0=xa0S, Se) compounds such as the lattice parameters were obtained from the structural optimization process (with the Perdew–Burke–Ernzerhof generalized gradient approximation), and they are in close agreement with the experimental lattice parameters. Conversely, calculations by the modified Becke Johnson exchange potential indicates that the Li2In2XY6 (Xxa0=xa0Si, Ge; Yxa0=xa0S, Se) compounds are semiconductors with direct energy band gaps. It is clearly observed from the DFT-calculated partial density of states, that there are significant contributions of the S-s and S-p states in the Li2In2SiS6 and Li2In2GeS6 compounds as well as the Se-s and Se-p states in the Li2In2SiSe6 and Li2In2GeSe6 compounds, respectively. The calculated band gaps ranging from 1.92xa0eV to 3.24xa0eV of the Li2In2XY6 (Xxa0=xa0Si, Ge; Yxa0=xa0S, Se) compounds are in good agreement with the experimental results, where the calculated band gap values are positioned in the visible region of the electromagnetic spectrum; therefore, these materials can be efficiently used for opto-electronic and optical applications. Furthermore, some general trends are observed in the optical responses of the compounds, which are possibly correlated to the energy band gaps when the X cations changes from Si to Ge and the Y anions changes from S to Se in the Li2In2XY6 (Xxa0=xa0Si, Ge; Yxa0=xa0S, Se) compounds, respectively.

Viscosity of a nanoconfined liquid during compression

The viscous behavior of liquids under nanoconfinement is not well understood. Using a small-amplitude atomic force microscope, we found bulk-like viscosity in a nanoconfined, weakly interacting liquid. A further decrease in viscosity was observed at confinement sizes of a just few molecular layers. Overlaid over the continuum viscous behavior, we measured non-continuum stiffness and damping oscillations. The average stiffness of the confined liquid was found to scale linearly with the size of the confining tip, while the damping scales with the radius of curvature of the tip end.

NaCl-dependent ordering and dynamic mechanical response in nanoconfined water.

Understanding the dynamics of water under nanoscale confinement is important for biology, geology, tribology, and nanotechnology. In many naturally occurring situations, ions are present in water at various concentrations. Here we report on how the addition of sodium ions alters the squeeze-out behavior of water nanoconfined between a mica surface and silicon oxide tip. We find that Na+ ions enhance molecular ordering and lead to longer mechanical relaxation times. We also observed a critical ion concentration, above which the confined water switches from a viscous to an elastic (solid-like) response at very slow, quasistatic compression speeds.

Simultaneous normal and shear measurements of nanoconfined liquids in a fiber-based atomic force microscope

We have developed an atomic force microscopy (AFM) technique that can perform simultaneous normal and shear stiffness measurements of nanoconfined liquids with angstrom-range amplitudes. The AFM technique is based on a fiber-interferometric, small-amplitude, off-resonance AFM. This AFM is capable of providing linear quasistatic measurements of the local mechanical properties of confined liquid layers while only minimally disturbing the layers themselves. A detailed analysis of the measurement geometry reveals that shear stiffness measurements are extremely challenging, as even small deviations from perfect orthogonality can lead to data that is very difficult to interpret. We will show ways out of this dilemma and present results that show simultaneous measurement of the shear and normal stiffness of confined liquid layers.

Squeeze-out dynamics of nanoconfined water: A detailed nanomechanical study.

In this study, we present a detailed analysis of the squeeze-out dynamics of nanoconfined water confined between two hydrophilic surfaces measured by small-amplitude dynamic atomic force microscopy. Explicitly considering the instantaneous tip-surface separation during squeeze-out, we confirm the existence of an adsorbed molecular water layer on mica and at least two hydration layers. We also confirm the previous observation of a sharp transition in the viscoelastic response of the nanoconfined water as the compression rate is increased beyond a critical value (previously determined to be about 0.8 nm/s). We find that below the critical value, the tip passes smoothly through the molecular layers of the film, while above the critical speed, the tip encounters pinning at separations where the film is able to temporarily order. Preordering of the film is accompanied by increased force fluctuations, which lead to increased damping preceding a peak in the film stiffness once ordering is completed. We analyze the data using both Kelvin-Voigt and Maxwell viscoelastic models. This provides a complementary picture of the viscoelastic response of the confined water film.

Ab-initio prediction of structural, electronic and magnetic properties of Hexafluoromanganete(IV) complexes

In this work, detailed electronic structure calculations of alkali metal fluorides A2MnF6 (A = K, Rb, Cs) have been performed using ab-initio calculating techniques based on density functional theory (DFT). We applied different exchange correlation functionals, namely Wu–Cohen generalized gradient approximation (WC-GGA), modified Becke Johnson potential (mBJ) and GGA plus Hubbard U method in order to treat the exchange correlation energy. The calculated lattice constants are found in excellent agreement with earlier experimental results. The electronic band structure and density of states show that Cs2MnF6 is half metallic, exhibiting semiconductivity in spin up direction and metallic behavior in spin down direction. The compounds, K2MnF6 and Rb2MnF6, are predicted as wide bandgap materials. The DFT + U method gives quite accurate results of the electronic bandgap as compared with other approximations. The states Mn-3d and F-2p contribute largely to the conduction and valence energy bands. Additionally, m...