arXiv subjects

Titus Masese

Publications and source records attributed to Titus Masese.

At least 19 recordsLinked to original sources

arXiv2024

Hilbert-P\'{o}lya conjecture via critical pseudo-magnetic degrees of freedom

Motivated by a recent pseudo-spin model for monolayer-bilayer phase transitions in silver-based honeycomb layered materials, we propose that the critical pseudo-magnetic fields in such systems correspond to both the infinite-channel Feshbach resonance widths of a (Fermi-Dirac/Bose-Einstein/etc.) condensate in 2 dimensions, and equivalently to the Lee-Yang zeros of the Ising model of two pseudo-spins with a partition function corresponding to a class of functions that must include the Riemann Xi function. Identifying the quantum-mechanical operator that yields the discontinuous/random/topological spectrum of the critical pseudo-magnetic fields in such systems offers a tenable realisation of the Hilbert-P\'{o}lya conjecture.

cond-mat.mtrl-sci↗

arXiv2024

Exploring $\rm Mg^{2+}$ and $\rm Ca^{2+}$ Conductors Via Solid-State Metathesis Reactions

The scarcity of viable electrode and electrolyte materials vastly hinders the advancement of magnesium and calcium batteries. This study utilises solid-state metathetical reactions involving chalcogen- and pnictogen-based honeycomb layered oxides with alkaline-earth halides/nitrates to synthesise $\rm Mg^{2+}$- and $\rm Ca^{2+}$-based materials previously achievable only under high-temperature/high-pressure conditions, as well as new metastable materials with unique crystal versatility. Particularly, we employ metathetical reactions involving $\rm Li_4MgTeO_6$, $\rm Na_2Mg_2TeO_6$, and $\rm Na_4MgTeO_6$ with $\rm MgCl_2$/$\rm MgSO_4$/$\rm Mg(NO_3)_2$.$\rm 6H_2O$ or $\rm Ca(NO_3)_2$.$\rm 4H_2O$ / $\rm CaCl_2$.$\rm 2H_2O$ at temperatures not exceeding 500 $^\circ$C to produce $\rm Mg_3TeO_6$ polymorphs, ilmenite-type $\rm CaMg_2TeO_6$/$\rm Mg_2CaTeO_6$, and double perovskite-type $\rm Ca_2MgTeO_6$. Thus, we demonstrate that these materials, conventionally requiring gigascale pressures or high temperatures (>1000$^\circ$C) for their proper synthesis, are now readily accessible at ambient pressure and considerably lower temperatures. Meanwhile, despite sub-optimal pellet densities, the synthesised ilmenite-type \magenta {$\rm Mg_3TeO_6$ (high-pressure polymorph)} and double perovskite-type ${\rm Ca}_2M{\rm TeO_6}$ ($M = \rm Mg, Ca, Zn$) materials exhibit remarkable bulk ionic conductivity at room temperature, marking them as promising compositional spaces for exploring novel $\rm Mg^{2+}$ and $\rm Ca^{2+}$ conductors. Furthermore, this study extends the applicability of metathetical reactions to attain Mg- or Ca-based antimonates, ruthenates, titanates, phosphates, and silicates, thus opening avenues to novel high-entropy multifunctional nanomaterial platforms with utility in energy storage and beyond.

cond-mat.mtrl-sci↗

arXiv2023

Advances in honeycomb layered oxides: Part I -- Syntheses and Characterisations of Pnictogen- and Chalcogen-Based Honeycomb Layered Oxides

Advancements in nanotechnology continue to unearth material vistas that presage a new age of revolutionary functionalities replete with unparalleled physical properties and avant-garde chemical capabilities that promise sweeping paradigm shifts in energy, environment, telecommunications and potentially healthcare. At the upper echelons of this realm, the pnictogen and chalcogen class of honeycomb layered oxides have emerged with fascinating crystal chemistry and exotic electromagnetic and topological phenomena that muster multifaceted concepts spanning from materials science to condensed matter physics and potential applications in electrochemistry, quantum mechanics and electronics. In a bid to shed light on the mechanisms governing these biomimetic nanostructures, this review highlights the significant milestones and breakthroughs that have augmented their current fundamental theory, properties, and utilities. Herein, we elucidate the vast promising crystal chemistry space against the backdrop of known synthesis and characterisation techniques employed in the development and optimisation of this class of honeycomb layered oxides. Further, we highlight key theoretical models that have reinvigorated the exploration and characterisation of within this class of materials and are poised to redefine the frontiers of material research and their applications. We conclude by envisaging future research directions where fascinating physicochemical, topological and electromagnetic properties could be lurking and where valiant efforts ought to be inclined, particularly in the prospective realisation of exotic material compositional space as well as their utility as testing grounds for emergent two-dimensional (2D) topological quantum gravity and conformal field theories.

cond-mat.mtrl-sci↗

arXiv2023

Honeycomb Layered Frameworks with Metallophilic Bilayers

This Review highlights the exciting advancements in the science of honeycomb layered frameworks with metallophilic bilayers that have recently garnered attention particularly due to reports of anomalous fractional valency states of silver cations sandwiched between transition metal slabs of other cations. First, the latest tactics and techniques including but not limited to X-ray absorption spectroscopy (XAS) and high-resolution transmission electron microscopy (HRTEM) particularly necessary for characterising recent honeycomb layered frameworks with metallophilic bilayers are described, with emphasis on silver-based oxides. Second, new strategies and concepts related to topochemically- or temperature-induced cationic-deficient phases expanding the compositional space of honeycomb layered frameworks focused on cationic bilayer architectures are also accentuated. Third, the latest condensed matter theoretic advances towards a full, atomistic description of the bilayered structure in such frameworks are detailed, especially related to critical phenomena at the cusp of the monolayer-bilayer phase transition. This entails, in part, describing honeycomb layered frameworks as optimised lattices within the congruent sphere packing problem, equivalent to a particular two-dimensional (2D) conformal field theory. Altogether, it is hoped that this Review will give the reader a panoramic view of the honeycomb layered frameworks with important applications within the emerging field of quantum matter, potentially redefining their frontier. Thus, the scope of this Review is expected to be worthwhile for recent graduates and emerging experts alike not only in the materials science and chemistry community but also in other diverse fields of interest.

cond-mat.mtrl-sci↗

arXiv2023

Pseudo-spin model of argentophilicity in honeycomb bilayered materials

We introduce a pseudo-spin model for the argentophilic bond expected in silver-based bilayered materials arising from a spontaneous pseudo-magnetic field interacting with pseudo-spins of two unconventional Ag ions, namely $\rm Ag^{2+}$ and $\rm Ag^{1-}$ electronically distinct from (albeit energetically degenerate to) the conventional $\rm Ag^{1+}$ cation typically observed in monolayered materials. This model suggests the possibility of tuning the dimensionality and hence the conductor-semiconductor-insulator properties of honeycomb bilayered materials by application of external fields, analogous to driving a superconducting or Coulomb blockade system to the normal regime by critical magnetic or electric fields respectively.

cond-mat.mes-hall↗

arXiv2023

Advances in honeycomb layered oxides: Part II -- Theoretical advances in the characterisation of honeycomb layered oxides with optimised lattices of cations

The quest for a successful condensed matter theory that incorporates diffusion of cations, whose trajectories are restricted to a honeycomb/hexagonal pattern prevalent in honeycomb layered materials is ongoing, with the recent progress discussed herein focusing on symmetries, topological aspects and phase transition descriptions of the theory. Such a theory is expected to differ both qualitatively and quantitatively from 2D electron theory on static carbon lattices, by virtue of the dynamical nature of diffusing cations within lattices in honeycomb layered materials. Herein, we have focused on recent theoretical progress in the characterisation of pnictogen- and chalcogen-based honeycomb layered oxides with emphasis on hexagonal/honeycomb lattices of cations. Particularly, we discuss the link between Liouville conformal field theory to expected experimental results characterising the optimal nature of the honeycomb/hexagonal lattices in congruent sphere packing problems. The diffusion and topological aspects are captured by an idealised model, which successfully incorporates the duality between the theory of cations and their vacancies. Moreover, the rather intriguing experimental result that a wide class of silver-based layered materials form stable Ag bilayers, each comprising a pair of triangular sub-lattices, suggests a bifurcation mechanism for the Ag triangular sub-lattices, which ultimately requires conformal symmetry breaking within the context of the idealised model, resulting in a cation monolayer-bilayer phase transition. Other relevant experimental, theoretical and computational techniques applicable to the characterisation of honeycomb layered materials have been availed for completeness.

cond-mat.mtrl-sci↗

arXiv2022

Honeycomb Layered Oxides With Silver Atom Bilayers and Emergence of Non-Abelian SU(2) Interactions

Honeycomb layered oxides with monovalent or divalent, monolayered cationic lattices generally exhibit myriad crystalline features encompassing rich electrochemistry, geometries and disorders, which particularly places them as attractive material candidates for next-generation energy storage applications. Herein, we report global honeycomb layered oxide compositions, ${\rm Ag_2}M_2{\rm TeO_6}$ ($M = \rm Ni, Mg, \textit{etc}.$) exhibiting $\rm Ag$ atom bilayers with sub-valent states within Ag-rich crystalline domains of ${\rm Ag_6}M_2{\rm TeO_6}$ and $\rm Ag$-deficient domains of ${\rm Ag}_{2 - x}\rm Ni_2TeO_6$ ($0 < x < 2$). The $\rm Ag$-rich material characterised by aberration-corrected transmission electron microscopy reveals local atomic structural disorders characterised by aperiodic stacking and incoherency in the bilayer arrangement of $\rm Ag$ atoms. Meanwhile, the global material not only displays high ionic conductivity, but also manifests oxygen-hole electrochemistry during silver-ion extraction. Within the $\rm Ag$-rich domains, the bilayered structure, argentophilic interactions therein and the expected $\rm Ag$ sub-valent states ($1/2+, 2/3+, \textit{etc}.$) are theoretically understood via spontaneous symmetry breaking of SU($2$)$\times$U($1$) gauge symmetry interactions amongst $3$ degenerate mass-less chiral fermion states, justified by electron occupancy of silver $4d_{z^2}$ and $5s$ orbitals on a bifurcated honeycomb lattice. This implies that bilayered frameworks have research applications that go beyond the confines of energy storage.

cond-mat.mtrl-sci↗

arXiv2022

Cationic vacancies as defects in honeycomb lattices with modular symmetries

Layered materials tend to exhibit intriguing crystalline symmetries and topological characteristics based on their two dimensional (2D) geometries and defects. We consider the diffusion dynamics of positively charged ions (cations) localized in honeycomb lattices within layered materials when an external electric field, non-trivial topologies, curvatures and cationic vacancies are present. The unit (primitive) cell of the honeycomb lattice is characterized by two generators, $J_1, J_2 \in \rm SL_2(\mathbb{Z})$ of modular symmetries in the special linear group with integer entries, corresponding to discrete re-scaling and rotations respectively. Moreover, applying a 2D conformal metric in an idealized model, we can consistently treat cationic vacancies as topological defects in an emergent manifold. The framework can be utilized to elucidate the molecular dynamics of the cations in exemplar honeycomb layered frameworks and the role of quantum geometry and topological defects not only in the diffusion process such as prediction of conductance peaks during cationic (de-)intercalation process, but also pseudo-spin and pseudo-magnetic field degrees of freedom on the cationic honeycomb lattice responsible for bilayers.

cond-mat.mtrl-sci↗

arXiv2022

On local conservation of information content in Schwarzschild black holes

The central equations in classical general relativity are the Einstein Field Equations, which accurately describe not only the generation of pseudo-Riemannian curvature by matter and radiation manifesting as gravitational effects, but more importantly mass-energy dynamics, evolution and distribution on the space-time manifold. Herein, we introduce a geometric phase in general relativity corresponding to Schwarzschild black hole information content. This quantity appropriately satisfies a local conservation law subject to minimal coupling, with other desirable properties such as the quantization of the black hole horizon in units of Planck area. The local conservation law is imposed by field equations, which not only contain the trace of Einstein Field Equations, but also a complex-valued function with properties analogous to the quantum-mechanical wave function. Such success attests to the utility of the proposed field equations in capturing key aspects of quantum gravity theories.

gr-qc↗

arXiv2022

Implications of Coordination Chemistry to Cationic Interactions in Honeycomb Layered Nickel Tellurates

Honeycomb layered tellurates represent a burgeoning class of multi-functional materials with fascinating crystal-structural versatility and a rich composition space. Despite their multifold capabilities, their compositional diversity remains underexplored due to complexities in experimental design and syntheses. Thus, in a bid to expand this frontier and derive relevant insights into allowed metastable compositions, we employ a density functional theory ($\rm DFT$) approach to predict $in$ $silico$ the crystal structures of new honeycomb layered tellurates embodied by the composition, $A\rm_2 Ni_2TeO_6$ ($A$ = alkali, hydrogen or coinage-metal cations). Here, alkali-metal atoms with vastly larger radii than $\rm K$ ($\rm Rb$ and $\rm Cs$) are found to engender a prismatic coordination with the oxygen atoms from the honeycomb slabs whilst coinage-metal atoms ($\rm Ag$, $\rm Au$ and $\rm Cu$) display a propensity for linear coordination. Further, $\rm H_2 Ni_2TeO_6$ is found to also render a linear coordination wherein the hydrogen atom preferentially establishes a stronger coordination with one of the oxygen atoms to form hydroxyl groups. All $A$ cations in the studied $A\rm_2 Ni_2TeO_6$ compositions form a honeycomb lattice. Conclusions on the possibility of a monolayer-bilayer phase transition in coinage metal atom tellurates can be drawn by considering the implications of conformal symmetry of the cation honeycomb lattice and metallophilicity. This work not only propounds new honeycomb layered tellurate compositions but also provides novel insight into the rational design of multifunctional materials for applications ranging from energy storage, catalysis and optics to analogue condensed matter systems of gravity.

cond-mat.mtrl-sci↗

arXiv2022

A Potential Cathode Material for Rechargeable Potassium-Ion Batteries Inducing Manganese Cation and Oxygen Anion Redox Chemistry: Potassium-Deficient $\rm K_{0.4}Fe_{0.5}Mn_{0.5}O_2$

Potassium-ion ($\rm K$-ion) rechargeable batteries; considered to be lucrative low-cost battery options for large-scale and capacious energy storage systems, have been garnering tremendous attention in recent years. However, due to the scarcity of cathode materials that can condone the reversible re-insertion of the large $\rm K$-ions at feasible capacities, the viability of $\rm K$-ion batteries has been greatly undercut. In this paper, we explore a potential cathode material in the $\rm K_2O$-$\rm Fe_2O_3$-$\rm MnO_2$ ternary phase system, that not only demonstrates reversible $\rm K$-ion reinsertion but also manifests relatively fast rate capabilities. The titled cathode compound, $\rm K_{0.4}Fe_{0.5}Mn_{0.5}O_2$, demonstrates a reversible capacity of approximately $\rm120 $ mAh g$^{-1}$ at $\rm 10$ hours of (dis)charge ($viz.$, $\rm C/10$ rate) with $ca.$ $\rm 85$% of the capacity being retained at a $\rm 1$ hour of (dis)charge ($\rm 1 C$ rate) which is considered to be good capacity retention. Additionally, both hard and soft X-rays have been employed to unravel the mechanism by which $\rm K$-ion is reversibly inserted into $\rm K_{0.4}Fe_{0.5}Mn_{0.5}O_2$. The results revealed a cumulative participation of both manganese cations and oxygen anions in $\rm K_{0.4}Fe_{0.5}Mn_{0.5}O_2$ illustrating its potential as a high-capacity $\rm K$-ion battery cathode material that relies on both anion and cation redox. Further development of related high-capacity cathode compositions can be anticipated.

cond-mat.mtrl-sci↗

arXiv2021

Sulfonylamide-Based Ionic Liquids for High-Voltage Potassium-Ion Batteries with Honeycomb Layered Cathode Oxides

The world is at the cusp of a new era where pivotal importance is being attached to the development of sustainable and high-performance energy storage systems. Potassium-ion batteries are deemed not only as cheap battery candidates, but also as the penultimate high-voltage energy storage systems within the monovalent-cation chemistries. However, their performance and sustainability are undermined by the lack of suitable electrolytes for high-voltage operation particularly due to the limited availability of cathode materials. Here, the potential of ionic liquids based on potassium bis(trifluoromethanesulfonyl)amide (KTFSA) as high-voltage electrolytes is presented by assessing their physicochemical properties, along with the electrochemical properties upon coupling with new high-voltage layered cathode materials. These ionic liquids demonstrate a lower redox potential for potassium dissolution / deposition (with a wide voltage tolerance of around $6.0$ $\rm V$), placing them as feasible and safe electrolytes for high-voltage potassium-ion battery configuration. This is proven by matching this electrolyte with new high-voltage layered cathode compositions, demonstrating stable electrochemical performance. The present findings of electrochemically stable ionic liquids based on potassium bis(trifluoromethanesulfonyl)amide will bolster further advancement of high-performance cathode materials, whose performance at high-voltage regimes were apparently restricted by the paucity of suitable and compatible electrolytes.

physics.chem-ph↗

arXiv2021

Coronene: A High-Voltage Anion De-insertion Cathode for Potassium-Ion Battery

Potassium-ion batteries have been envisioned to herald the age of low-cost and high-performance energy storage systems. However, the sparsity of viable components has dampened the progress of these energy devices. Thus, herein, we report coronene, a high-voltage cathode material that manifests a high-voltage of $4.1 \rm V$ enkindled by anion (de)insertion. This work not only illuminates the broad class of polycyclic aromatic hydrocarbons as prospective cathode materials but also sets a new benchmark for the performance of future organic cathode materials.

cond-mat.mtrl-sci↗

arXiv2021

Unveiling Structural Disorders in Honeycomb Layered Oxide: $\rm Na_2Ni_2TeO_6$

Honeycomb layered oxides have garnered tremendous research interest in a wide swath of disciplines owing not only to the myriad physicochemical properties they exhibit, but also their rich crystal structural versatility. Herein, a comprehensive crystallographic study of a sodium-based $\rm Na_2Ni_2TeO_6$ honeycomb layered oxide has been performed using atomic-resolution transmission electron microscopy, elucidating a plethora of atomic arrangement (stacking) disorders in the pristine material. Stacking disorders in the arrangement of honeycomb metal slab layers (stacking faults) occur predominantly perpendicular to the slabs with long-range coherence length and enlisting edge dislocations in some domains. Moreover, the periodic arrangement of the distribution of alkali atoms is altered by the occurrence of stacking faults. The multitude of disorders innate in $\rm Na_2Ni_2TeO_6$ envisage broad implications in the functionalities of related honeycomb layered oxide materials and hold promise in bolstering renewed interest in their material science.

cond-mat.mtrl-sci↗

arXiv2021

Topological Defects and Unique Stacking Disorders in Honeycomb Layered Oxide $\rm K_2Ni_2TeO_6$ Nanomaterials: Implications for Rechargeable Batteries

Endowed with a multitude of exquisite properties such as rich electrochemistry, superb topology and eccentric electromagnetic phenomena, honeycomb layered oxides have risen to the top echelons of science with applications in diverse fields ranging from condensed matter physics, solid-state chemistry, materials science, solid-state ionics to electrochemistry. However, these oxides are vastly underutilised as their underlying atomistic mechanisms remain unexplored. Therefore, in this study, atomic-resolution imaging on pristine $\rm K_2Ni_2TeO_6$ along multiple zone axes was conducted using spherical aberration-corrected scanning transmission electron microscopy (Cs-corrected STEM) to reveal hitherto unreported nanoscale topological defects and curvature which can be associated with various phase transitions. Furthermore, we discover the coexistence of a stacking variant with P3-type sequence alongside the well-reported P2-type stacking sequence in such honeycomb layered oxides. Our findings have the potential to inspire further experimental and theoretical studies into the role of stacking and topology in the functionality of honeycomb layered oxides, for instance, as high-performance electrode materials for rechargeable batteries.

cond-mat.mtrl-sci↗

arXiv2021

Mixed Alkali-Ion Transport and Storage in Atomic-Disordered Honeycomb Layered $\rm NaKNi_2TeO_6$

Honeycomb layered oxides constitute an emerging class of materials that show interesting physicochemical and electrochemical properties. However, the development of these materials is still limited. Here, we report the combined use of alkali atoms ($\rm Na$ and $\rm K$) to produce a mixed alkali honeycomb layered oxide material, namely, $\rm NaKNi_2TeO_6$. Via transmission electron microscopy measurements, we reveal the local atomic structural disorders characterised by aperiodic stacking and incoherency in the alternating arrangement of $\rm Na$ and $\rm K$ atoms. We also investigate the possibility of mixed electrochemical transport and storage of $\rm Na$ and $\rm K$ ions in $\rm NaKNi_2TeO_6$. In particular, we report an average discharge cell voltage of about $4\, \rm V$ and a specific capacity of around $80\, \rm mAh\, g^{-1}$ at low specific currents (i.e., $< 10\, \rm mA\, g^{-1}$) when a $\rm NaKNi_2TeO_6$-based positive electrode is combined with a room-temperature $\rm NaK$ liquid alloy negative electrode using an ionic liquid-based electrolyte solution. These results represent a step towards the use of tailored cathode active materials for dendrite-free electrochemical energy storage systems exploiting room-temperature liquid alkali metal alloy materials.

cond-mat.mtrl-sci↗

arXiv2021

An Idealised Approach of Geometry and Topology to the Diffusion of Cations in Honeycomb Layered Oxide Frameworks

Honeycomb layered oxides are a novel class of nanostructured materials comprising alkali or alkaline earth metals intercalated into transition metal slabs. The intricate honeycomb architecture and layered framework endows this family of oxides with a tessellation of features such as exquisite electrochemistry, unique topology and fascinating electromagnetic phenomena. Despite having innumerable functionalities, these materials remain highly underutilized as their underlying atomistic mechanisms are vastly unexplored. Therefore, in a bid to provide a more in-depth perspective, we propose an idealised diffusion model of the charged alkali cations (such as lithium, sodium or potassium) in the two-dimensional (2D) honeycomb layers within the three-dimensional (3D) crystal of honeycomb layered oxide frameworks. This model not only explains the correlation between the excitation of cationic vacancies (by applied electromagnetic fields) and the Gaussian curvature deformation of the 2D surface, but also takes into consideration, the quantum properties of the cations and their inter-layer mixing through quantum tunnelling. Through this work, we offer a novel theoretical framework for the study of 3D layered materials with 2D cationic diffusion currents, as well as providing pedagogical insights into the role of topological phase transitions in these materials in relation to Brownian motion and quantum geometry.

cond-mat.mtrl-sci↗

arXiv2021

Reproducing the asymptotic behaviour of galaxy rotation curves by a novel constraint in general relativity

The cold dark matter paradigm has been posited as the standard explanation for the non-Keplerian behavior of galaxy rotation curves, where for galaxies satisfying the Tully-Fisher relation, the mass of the dark matter halo from a large class of universal dark matter profiles ought to roughly increase linearly with radial distance at large distances, $m(r) \sim r/nG$ ($G$ is the gravitational constant and $n$ is a dimensionless parameter which depends on the amount of baryonic matter $M$ within the galaxy). Despite numerous advances in modeling galaxy formation and evolution, a scientific consensus on the origin of the observed dependence of the dimensionless parameter $n = (GMa_{0})^{-1/2}$ on the mass of baryonic matter $M$ within the galaxy (the Tully-Fisher relation), and the connection of the cosmological constant $Λ$ to the parameter $a_{0} \sim (Λ/3)^{1/2}$ remains elusive. Here, we show that Einstein Field Equations can be remolded into $\nabla_ν\mathcal{K}^ν_{\,\,μ} = 8πGMΨ^{*}\mathcal{D}_μΨ$, where $\mathcal{K}_{μν}$ is a complex Hermitian tensor, $\mathcal{D}_μ$ is a covariant derivative and $Ψ$ is a complex-valued function. This avails a novel constraint, $\nabla_μ\nabla_ν\mathcal{K}^{μν} = 0$ not necessarily available in Einstein's General Relativity. In the weak-field regime, we can readily reproduce the Tully-Fisher relation using the usual charge-less pressure-less fluid. Moreover, our approach is equivalent to a Ginzburg-Landau theory of $n$ bosons, where the order parameter is normalized as $\int_{0}^{1/a_{0}} dr\,4πr^2Ψ^*Ψ= n$ and $1/a_{0} \sim (Λ/3)^{-1/2}$ is the cut-off length scale comparable to the size of the de Sitter universe. Our investigations provide a framework that reproduces the mass-asymptotic speed relation in galaxies within the cold dark matter paradigm.

gr-qc↗