arXiv subjects

Shogo Kawaguchi

Publications and source records attributed to Shogo Kawaguchi.

7 recordsLinked to original sources

arXiv2026

Survival of the metallic state in a single-hole multiband $p$-orbital molecular system

Strong correlations and ferromagnetic Hund's coupling lead to diverse electronic phenomena in transition-metal oxides that sensitively depend on the $d$-orbital electron filling. Fullerides, their $p$-electron counterparts, exhibit effective antiferromagnetic Hund's coupling in a different energy range. At half-filling ($n=3$, three electrons in triply degenerate orbitals), both $d-$ and $p$-electron systems are Mott insulators due to strong correlations and Hund's coupling. Away from half-filling, in single-electron/hole ($n=1,5$) $d$-orbital systems, Hund's coupling opposes the correlations, reducing the Mott gap and allowing survival of metallicity. Here we report a single-hole multiorbital correlated $p$-electron system, orthorhombic-structured Yb$_2$CsC$_{60}$ comprising pentavalent C$_{60}^{5-}$ anions, which also exhibits a robust metallic state with no Mott transition, just like in the metastable single-electron cubic-structured CsC$_{60}$. We assert that particle-hole symmetry holds well in ($n=1,5$) fullerides and that their $p$-electron-derived states are analogous to those in $d$-orbital solids, providing impetus for further study of these correlated systems.

cond-mat.str-el↗

arXiv2026

Time-Temperature-Transformation (TTT) Diagrams to rationalize the nucleation and quenchability of metastable $α$-Li$_3$PS$_4$

$α$-Li$_3$PS$_4$ is a promising solid-state electrolyte with the highest ionic conductivity among its polymorphs. However, its formation presents a thermodynamic paradox: the $α$-phase is the equilibrium phase at high temperature and transforms to the stable $γ$-Li$_3$PS$_4$ polymorph when cooled to room temperature; however, $α$-Li$_3$PS$_4$ can be synthesized and quenched in a metastable state via rapid heating at relatively low temperatures. The origin of this synthesizability and anomalous stability has remained elusive. Here, we resolve this paradox by establishing a comprehensive time-temperature-transformation (TTT) diagram, constructed from a computational temperature-size phase diagram and experimental high-time-resolution isothermal measurements. Our density functional theory calculations reveal that at the nanoscale, the $α$-phase is stabilized by its low surface energy, which drastically lowers the nucleation barrier across a wide temperature range. This size-dependent stabilization is directly visualized using in-situ synchrotron X-ray diffraction and electron microscopy, capturing the rapid nucleation of nano-sized $α$-phase and its subsequent slow transformation. This work presents a generalizable framework that integrates thermodynamic and kinetic factors for understanding nucleation and phase transformation mechanisms, providing a rational strategy for the targeted synthesis of functional metastable materials.

cond-mat.mtrl-sci↗

arXiv2025

Control of Covalent Bond Enables Efficient Magnetic Cooling

Magnetic cooling, harnessing the temperature change in matter when exposed to a magnetic field, presents an energy-efficient and climate-friendly alternative to traditional vapor-compression refrigeration systems, with a significantly lower global warming potential. The advancement of this technology would be accelerated if irreversible losses arising from hysteresis in magnetocaloric materials were minimized. Despite extensive efforts to manipulate crystal lattice constants at the unit-cell level, mitigating hysteresis often compromises cooling performance. Herein, we address this persistent challenge by forming Sn(Ge)3/Sn(Ge)3 bonds within the unit cell of the Gd5Ge4 compound. Our approach enables an energetically favorable phase transition, leading to the elimination of thermal hysteresis. Consequently, we achieve a synergistic improvement of two key magnetocaloric figures of merit: a larger magnetic entropy change and a twofold increase in the reversible adiabatic temperature change (from 3.8 to 8 K) in the Gd5Sn2Ge2 compound. Such synergies can be extended over a wide temperature range. This study demonstrates a paradigm shift in mastering hysteresis toward simultaneously achieving exceptional magnetocaloric metrics and opens up promising avenues for gas liquefaction applications in the longstanding pursuit of sustainable energy solutions.

cond-mat.mtrl-sci↗

arXiv2025

Impact of in-plane disorders on the thermal conductivity of AgCrSe$_2$

Superionic conductors have recently attracted renewed attention for their use as thermoelectric materials due to their extremely low lattice thermal conductivity. Of central interest is why the superionic conductors exhibit such low thermal conductivity, and competing mechanisms have been proposed thus far. In this study, we investigate the effects of Cu and Au substitution for Ag site on the crystal structure and thermal properties of AgCrSe$_2$, which exhibits superionic conduction of Ag ions. We show that Au substitution significantly reduces the lattice thermal conductivity of AgCrSe$_2$. Powder structure analysis using synchrotron x-ray diffraction reveals that Au substitution increases the anisotropic atomic displacement parameter of Ag ions along the $a$ and $b$ axes. This result indicates that the amplitude of in-plane vibrations is enhanced, which is attributed to increased anharmonicity in the potential energy around Ag ions. The enhanced vibrational amplitude also suggests a reduction in the force constants between Ag ions. Consequently, the enhanced anharmonicity not only shortens the phonon lifetime ($τ$) by increasing phonon-phonon scattering, but also increases the number of low-energy phonons, which further contributes to the reduction of $τ$. This anharmonicity mechanism is applicable to other superionic conductors exhibiting ultra-low thermal conductivity, promoting their widespread use as thermoelectric materials.

cond-mat.mtrl-sci↗

arXiv2025

Mixed anion control of enhanced negative thermal expansion in the oxysulfide of PbTiO3

The rare physical property of negative thermal expansion (NTE) is intriguing because materials with large NTE over a wide temperature range can serve as high-performance thermal expansion compensators. However, applications of NTE are hindered by the fact that most of the available NTE materials show small magnitudes of NTE, and/or NTE occurs only in a narrow temperature range. Herein, for the first time, we investigated the effect of anion substitution instead of general Pb/Ti-site substitutions on the thermal expansion properties of a typical ferroelectric NTE material, PbTiO3. Intriguingly, the substitution of S for O in PbTiO3 further increases the tetragonality of PbTiO3. Consequently, an unusually enhanced NTE with an average volumetric coefficient of thermal expansion $\barα_V$ = -2.50 $\times$ 10$^{-5}$/K was achieved over a wide temperature range (300 -- 790 K), which is contrasted to that of pristine PbTiO3 ($\barα_V$ = -1.99 $\times$ 10$^{-5}$/K RT -- 763 K). The intensified NTE is attributed to the enhanced hybridization between Pb/Ti and O/S atoms by the substitution of S, as evidenced by our theoretical investigations. We therefore demonstrate a new technique for introducing mixed anions to achieve large NTE over a wide temperature range in PbTiO3-based ferroelectrics.

cond-mat.mtrl-sci↗

arXiv2021

Barocaloric thermal batteries

Nowadays the world is facing a prominent paradox regarding thermal energy. The production of heat accounts for more than 50% of global final energy consumption while the waste heat potential analysis reveals that 72% of the global primary energy consumption is lost after conversion mainly in the form of heat. Towards global decarbonization, it is of vital importance to establish a solution to thermal energy utilization under full control. Here, we propose and realize an unprecedented concept -- barocaloric thermal batteries based on the inverse colossal barocaloric effect of NH4SCN. Thermal charging is initialized upon pressurization through an order-to-disorder phase transition below 364 K and in turn the discharging of 43 J g-1, which are eleven times more than the input mechanical energy, occurs on demand at depressurization at lower temperatures. The discharging is also manifested as a directly measured temperature rise of 12 K. The thermodynamic equilibrium nature of the pressure-restrained heat-carrying phase guarantees stable storage and/or transport over a variety of temporal and/or spatial scales. The barocaloric thermal batteries reinforced by their solid microscopic mechanism are expected to significantly advance the ability to take advantage of waste heat.

cond-mat.mtrl-sci↗

arXiv2019

Machine learning clustering technique applied to powder X-ray diffraction patterns to distinguish alloy substitutions

We applied the clustering technique using DTW (dynamic time wrapping) analysis to XRD (X-ray diffraction) spectrum patterns in order to identify the microscopic structures of substituents introduced in the main phase of magnetic alloys. The clustering is found to perform well to identify the concentrations of the substituents with successful rates (around 90%). The sufficient performance is attributed to the nature of DTW processing to filter out irrelevant informations such as the peak intensities (due to the incontrollability of diffraction conditions in polycrystalline samples) and the uniform shift of peak positions (due to the thermal expansions of lattices).

physics.comp-ph↗