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Register a new userSuperionic liquids in conducting nanoslits: A variety of phase transitions and ensuing charging behavior
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We develop a theory of charge storage in ultra-narrow slit-like pores of nano-structured electrodes. Our analysis is based on the Blume-Capel model in external field, which we solve analytically on a Bethe lattice. The obtained solutions allow us to explore the complete phase diagram of confined ionic liquids in terms of the key parameters characterising the system, such as pore ionophilicity, interionic interaction energy and voltage. The phase diagram includes the lines of first and second-order, direct and re-entrant, phase transitions, which are manifested by singularities in the corresponding capacitance-voltage plots. To test our predictions experimentally requires mono-disperse, conducting, ultra-narrow slit pores, permitting only one layer of ions, and thick pore walls, preventing interionic interactions across the pore walls. However, some qualitative features, which distinguish the behavior of ionophilic and ionophobic pores, and its underlying physics, may emerge in future experimental studies of more complex electrode structures.
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The ion-ion interactions become exponentially screened for ions confined in ultranarrow metallic pores. To study the phase behaviour of an assembly of such ions, called a superionic liquid, we develop a statistical theory formulated on bipartite lattices, which allows an analytical solution within the Bethe-lattice approach. Our solution predicts the existence of ordered and disordered phases in which ions form a crystal-like structure and a homogeneous mixture, respectively. The transition between these two phases can potentially be first or second order, depending on the ion diameter, degree of confinement and pore ionophobicity. We supplement our analytical results by three-dimensional off-lattice Monte Carlo simulations of an ionic liquid in slit nanopores. The simulations predict formation of ionic clusters and ordered snake-like patterns, leading to characteristic close-standing peaks in the cation-cation and anion-anion radial distribution functions.
The phase transitions of random-field q-state Potts models in d=3 dimensions are studied by renormalization-group theory by exact solution of a hierarchical lattice and, equivalently, approximate Migdal-Kadanoff solutions of a cubic lattice. The recursion, under rescaling, of coupled random-field and random-bond (induced under rescaling by random fields) coupled probability distributions is followed to obtain phase diagrams. Unlike the Ising model (q=2), several types of random fields can be defined for q >= 3 Potts models, including random-axis favored, random-axis disfavored, random-axis randomly favored or disfavored cases, all of which are studied. Quantitatively very similar phase diagrams are obtained, for a given q for the three types of field randomness, with the low-temperature ordered phase persisting, increasingly as temperature is lowered, up to random-field threshold in d=3, which is calculated for all temperatures below the zero-field critical temperature. Phase diagrams thus obtained are compared as a function of $q$. The ordered phase in the low-q models reaches higher temperatures, while in the high-q models it reaches higher random fields. This renormalization-group calculation result is physically explained.
Dimensionless ratios of physical properties can characterize low-temperature phases in a wide variety of materials. As such, the Wilson ratio (WR), the Kadowaki-Woods ratio and the Wiedemann--Franz law capture essential features of Fermi liquids in metals, heavy fermions, etc. Here we prove that the phases of many-body interacting multi-component quantum liquids in one dimension (1D) can be described by WRs based on the compressibility, susceptibility and specific heat associated with each component. These WRs arise due to additivity rules within subsystems reminiscent of the rules for multi-resistor networks in series and parallel --- a novel and useful characteristic of multi-component Tomonaga-Luttinger liquids (TLL) independent of microscopic details of the systems. Using experimentally realised multi-species cold atomic gases as examples, we prove that the Wilson ratios uniquely identify phases of TLL, while providing universal scaling relations at the boundaries between phases. Their values within a phase are solely determined by the stiffnesses and sound velocities of subsystems and identify the internal degrees of freedom of said phase such as its spin-degeneracy. This finding can be directly applied to a wide range of 1D many-body systems and reveals deep physical insights into recent experimental measurements of the universal thermodynamics in ultracold atoms and spins.
Lattice dynamics and molecular dynamics studies of the oxides UO2 and Li2O in their normal as well as superionic phase are reported. Lattice dynamics calculations have been carried out using a shell model in the quasiharmonic approximation. The calculated elastic constants, phonon frequencies and specific heat are in good agreement with reported experimental data, which help validate the interatomic potentials required for undertaking molecular dynamics simulations. The calculated free energies reveal high pressure fluorite to cottunite phase transitions at 70 GPa for UO2 and anti-fluorite to anti-cotunnite phase transformation at 25 GPa for Li2O, in agreement with reported experiments. Molecular dynamics studies shed important insights into the mechanisms of diffusion and superionic behavior at high temperatures. The calculated superionic transition temperature of Li2O is 1000 K, while that of UO2 is 2300 K.
Active matter is not only indispensable to our understanding of diverse biological processes, but also provides a fertile ground for discovering novel physics. Many emergent properties impossible for equilibrium systems have been demonstrated in active systems. These emergent features include motility-induced phase separation, long-ranged ordered (collective motion) phase in two dimensions, and order-disorder phase co-existences (banding and reverse-banding regimes). Here, we unify these diverse phase transitions and phase co-existences into a single formulation based on generic hydrodynamic equations for active fluids. We also reveal a novel co-moving co-existence phase and a putative novel critical point.
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