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Kenichiro Koga

Publications and source records attributed to Kenichiro Koga.

7 recordsLinked to original sources

Critical exponents of fluid-fluid interfacial tensions near a critical endpoint in a nonwetting gap

Fluid three-phase equilibria, with phases $\alpha, \beta, \gamma$, are studied close to a tricritical point, analytically and numerically, in a mean-field density-functional theory with two densities. Employing Griffiths' scaling for the densities, the interfacial tensions of the wet and nonwet interfaces are analysed. The mean-field critical exponent is obtained for the vanishing of the critical interfacial tension $\sigma_{\beta\gamma}$ as a function of the deviation of the noncritical interfacial tension $\sigma_{\alpha\gamma}$ from its limiting value at a critical endpoint $\sigma_{\alpha,\beta\gamma}$. In the wet regime, this exponent is $3/2$ as expected. In the nonwetting gap of the model, the exponent is again $3/2$, except for the approach to the critical endpoint on the neutral line where $\sigma_{\alpha\beta} = \sigma_{\alpha\gamma}$. When this point is approached along any path with $\sigma_{\alpha\beta} \neq \sigma_{\alpha\gamma}$, or along the neutral line, $\sigma_{\beta\gamma} \propto | \sigma_{\alpha\gamma} - \sigma_{\alpha,\beta\gamma}|^{3/4}$, featuring an anomalous critical exponent $3/4$, which is an exact result derived by analytic calculation and explained by geometrical arguments.

cond-mat.stat-mech

Interplay of Coil-Globule Transitions and Aggregation in Homopolymer Aqueous Solutions: Simulation and Topological Insights

We investigate the structural and topological properties of hydrophobic homopolymer chains in aqueous solutions using molecular dynamics simulations and circuit topology (CT) analysis. By combining geometric observables, such as radius of gyration and degree of aggregation, with CT data, we capture the relationship between coil-globule and aggregation transitions, resolving the system's structural changes with temperature. Our results reveal a temperature-driven collective transition from isolated coiled chains to globular aggregates. At a characteristic transition temperature $T_c$, each chain in multichain systems undergoes a rapid coil-globule collapse, coinciding with aggregation, in contrast to the gradual collapse observed in single-chain systems at infinite dilution. This collective transition is reflected in geometric descriptors and a reorganization of CT motifs, shifting from intrachain-dominated motifs at low temperatures to a diverse ensemble of multichain motifs at higher temperatures. CT motif enumeration provides contact statistics while offering a topologically detailed view of polymer organization. These findings highlight CT's utility as a structural descriptor for polymer systems and suggest applications to biopolymer aggregation and folding.

cond-mat.soft

Ferroaxial order of the monolayer ice in martyite

Ice Ih, the most stable phase of water at ambient pressure, is a stacking of the honeycomb network of water molecules H2O. What if one layer of ice is exfoliated and confined to a two-dimensional (2D) sheet? Martyite Zn3(V2O7)(OH)2 2H2O, a mineral with the honeycomb lattice of H2O in the porous framework, is an ideal system for studying such monolayer ice. Due to the geometrical frustration and 2D nature, H2O molecules are dynamically disordered at room temperature. In this study, we reveal disorder-order transitions of H2O in martyite using single-crystal x-ray diffraction (XRD). The XRD results visualize the formation of hydrogen-bonded toroidal H2O hexamers, leading to the ferroaxial order below 200 K. Combined with the molecular dynamics simulations, we discuss the formation process of the H2O hexamers and how they compromise the molecular arrangement towards lower temperatures. Our results unveil the ground state of monolayer ice, a fundamental knowledge to understand the polymorphism of H2O.

cond-mat.mtrl-sci

The nature of the hydrophobic interaction varies as the solute size increases from methane's to C60's

The hydrophobic interaction, often combined with the hydrophilic or ionic interactions, makes the behavior of aqueous solutions very rich and plays an important role in biological systems. Theoretical and computer simulation studies haven shown that the water-mediated force depends strongly on the size and other chemical properties of the solute, but how it changes with these factors remains unclear. We report here a computer simulation study that illustrates how the hydrophobic pair interaction and the entropic and enthalpic terms change with the solute size when the solute-solvent weak attractive interaction is unchanged with the solute size. The nature of the hydrophobic interaction changes qualitatively as the solute size increases from that of methane to that of fullerene. The potential of mean force between small solutes has several well-defined extrema including the third minimum whereas the potential of mean force between large solutes has the deep contact minimum and the large free-energy barrier between the contact and the water-bilayer separated configurations. The difference in the potential of mean force is related to the differences in the water density, energy, and hydrogen bond number distributions in the vicinity of the pairs of hydrophobic solutes.

cond-mat.soft

Wetting and nonwetting near a tricritical point

The dihedral contact angles between interfaces in three-fluid-phase equilibria must be continuous functions of the bulk thermodynamic fields. This general argument, which we propose, predicts a nonwetting gap in the phase diagram, challenging the common belief in "critical-point wetting", even for short-range forces. A demonstration is provided by exact solution of a mean-field two-density functional theory for three-phase equilibria near a tricritical point (TCP). Complete wetting is found in a tiny vicinity of the TCP. Away from it, nonwetting prevails and no wetting transition takes place, not even when a critical endpoint is approached. Far from the TCP, reentrant wetting may occur, with a different wetting phase. These findings shed light on hitherto unexplained experiments on ternary water-oil-nonionic amphiphile mixtures in which nonwetting continues to exist as one approaches either one of the two critical endpoints.

cond-mat.stat-mech

Theory of electrolytes including steric, attractive, and hydration interactions

We present a continuum theory of electrolytes composed of a waterlike solvent and univalent ions. First, we start with a density functional $\cal F$ for the coarse-grained solvent, cation, and anion densities, including the Debye-Hückel free energy, the Coulombic interaction, and the direct interactions among these three components. These densities fluctuate obeying the distribution $\propto \exp(- {\cal F}/k_BT)$. Eliminating the solvent density deviation in $\cal F$, we obtain the effective non-Coulombic interactions among the ions, which consist of the direct ones and the solvent-mediated ones. %where the latter are written in terms of the ion volumes %and are inversely proportional to the solvent compressibility. We then derive general expressions for the ion correlation, the apparent partial volume, and the activity and osmotic coefficients up to linear order in the average salt density $n_{\rm s}$. Secondly, we perform numerical analysis using the Mansoori-Carnahan-Starling-Leland model $[$J. Chem. Phys. {\bf 54}, 1523 (1971)$]$ for three-component hardspheres. The effective interactions sensitively depend on the cation and anion sizes due to competition between the steric and hydration effects, which are repulsive between small-large ion pairs and attractive between symmetric pairs. These agree with previous experiments and Collins' rule $[$Biophys. J. {\bf 72}, 65 (1997)$]$. We also give simple approximate expressions for the ionic interaction coefficients valid for any ion sizes.

cond-mat.soft

Three-phase equilibria in density-functional theory: interfacial tensions

A mean-field density-functional model for three-phase equilibria in fluids (or other soft condensed matter) with two spatially varying densities is analyzed analytically and numerically. The interfacial tension between any two out of three thermodynamically coexisting phases is found to be captured by a surprisingly simple analytic expression that has a geometric interpretation in the space of the two densities. The analytic expression is based on arguments involving symmetries and invariances. It is supported by numerical computations of high precision and it agrees with earlier conjectures obtained for special cases in the same model. An application is presented to three-phase equilibria in the vicinity of a tricritical point. Using the interfacial tension expression and employing the field variables compatible with tricritical point scaling, the expected mean-field critical exponent is derived for the vanishing of the critical interfacial tension as a function of the deviation of the noncritical interfacial tension from its limiting value, upon approach to a critical endpoint in the phase diagram. The analytic results are again confirmed by numerical computations of high precision.

cond-mat.stat-mech