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Hema Teherpuria

Publications and source records attributed to Hema Teherpuria.

3 recordsLinked to original sources

A molecular dynamics study of surface-directed spinodal decomposition on a chemically patterned amorphous substrate

We employ a molecular dynamics (MD) study to explore pattern selection in binary fluid mixtures ($AB$) undergoing surface-directed spinodal decomposition on a chemically patterned amorphous substrate. We chose a checkerboard pattern with chemically distinct square patches of a side $M$, with neighboring patches preferring different particle types. We report the efficient transposition of the substrate's pattern as a \emph{registry} to the fluid cross sections in its vicinity when the pattern's periodicity $λ/σ\simeq 2M$ ($σ$ being the fluid particle size) is larger than the mixture's spinodal length scale $λ_c/σ\simeq 2π/ξ_B$ ($ξ_B$ being the bulk correlation length). Our correlation analysis between the surface field and the surface-\emph{registries} in the substrate's normal direction shows that the associated decay length, $L_{\perp}(t)$, increases with decreasing pattern periodicity ($λ$). $L_{\perp}(t)$ also exhibits diffusive growth with time $\sim t^{1/3}$, similar to wetting-layer growth for chemically homogeneous walls. Our MD results also show the emergence of composition waves parallel to the substrate, whose wavelength exhibits dynamical scaling with a power-law growth in time $L_{||}(z,t)\sim t^α$. $L_{||}(z,t)$ shows dynamical crossovers from a transient \emph{surface-registry} regime to universal \emph{phase-separation} regimes for cross-sections with \emph{registries}. We also give an account of the scaling of \emph{registry's} formation and melting times with patch sizes.

cond-mat.soft↗

Salt Effects on Ionic Conductivity Mechanisms in Ethylene Carbonate Electrolytes: Interplay of Viscosity and Ion-ion Relaxations

The intricate role of shear viscosity and ion-pair relaxations on ionic conductivity mechanisms and the underlying changes induced by salt concentration ($c$) in organic liquid electrolytes remain poorly understood despite their widespread technological importance. Using molecular dynamics simulations employing nonpolarizable force fields for $c$ ranging between 10$^{-3}$ to 10$^1$ M, we show that the low and high $c$ regimes of the EC-LiTFSI electrolytes are distinctly characterized by $η\simτ_c^{1/2}$ and $η\simτ_c^{1}$, where $η$ and $τ_c$ are shear viscosity and cation-anion relaxation timescales, respectively. Our extensive simulations and analyses suggest a universal relationship between the ionic conductivity and $c$ as $σ(c)\sim c^αe^{-c/c_{0}} (α>0)$. The proposed relationship convincingly explains the ionic conductivity over a wide range of $c$, where the term $c^α$ accounts for the uncorrelated motion of ions and $e^{-c/c_0}$ captures the salt-induced changes in shear viscosity. Our simulations suggest vehicular mechanism to be dominant at low $c$ regime which transitions into a structural diffusion mechanism at high $c$ regime, where structural relaxation is the dominant form of ion transport mechanism. Our findings shed light on some of the fundamental aspects of the ion conductivity mechanisms in liquid electrolytes, offering insights into optimizing the ion transport in EC-LiTFSI electrolytes.

cond-mat.soft↗

Ion Transport Mechanisms in Pectin-containing EC-LiTFSI Electrolytes

Using all-atom molecular dynamics simulations, we report the structure and ion transport characteristics of a new class of solid polymer electrolytes that contain biodegradable and mechanically stable biopolymer pectin. We simulate a highly conducting ethylene carbonate (EC) as a solvent for lithium-trifluoromethanesulfonimide (LiTFSI) salt containing different weight percentages of pectin. Our simulations reveal that the pectin chains reduce the coordination numbers of lithium ions around the counterions (and vice-versa) because of stronger lithium-pectin interactions compared to lithium-TFSI interactions. Further, the pectin is found to promote smaller ionic aggregates over larger ones, contrary to results typically reported for liquid and polymer electrolytes. We observe that the loading of pectin in EC-LiTFSI electrolytes increases the viscosity ($η$) and relaxation timescales ($τ_c$), indicating higher mechanical stability and, consequently, the mean squared displacements, diffusion coefficients (D), and the Nernst-Einstein conductivity ($σ_{NE}$) decrease. Interestingly, while the lithium diffusivities are related to the ion-pair relaxation timescales as $D_+\sim τ_c^{-3.1}$, the TFSI$^-$ diffusivities exhibit excellent correlations with ion-pair relaxation timescales as $D_-\sim τ_c^{-0.95}$. On the other hand, the NE conductivities are dictated by distinct transport mechanisms and scales with ion-pair relaxation timescale as $σ_{NE}\sim τ_c^{-1.85}$.

cond-mat.soft↗