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The elucidation of chemical bonding, coupled with an exploration of the correlated dynamics of constituent atoms, is essential for unravelling the underlying mechanism responsible for low lattice thermal conductivity (κL) exhibited by a crystalline solid, which is essential for thermoelectrics and thermal barrier coatings. In this regard, Pauling's third empirical rule, which deals with the cationic repulsion due to proximity in the face or edge shared polyhedra in a crystal structure, can bring about the lattice instability required to suppress the κL. Here, we demonstrate the presence of such instability in a ternary selenide, TlAgSe, leading to a ultra‐low κL of 0.17 W/m.K at 573 K. Our study reveals the instability arising from Ag−Ag repulsion within edge‐shared AgSe4 tetrahedra through investigation of the local structure using synchrotron X‐ray pair distribution function (PDF) analysis and supported by first‐principles density functional theory calculations. We observe correlation between weakening in the Ag and the Tl‐sublattice, providing direct experimental evidence of Pauling's third empirical rule. The correlated rattling of Ag and Tl induces a highly anharmonic lattice and low energy optical phonons, resulting in suppressed sound velocity and ultralow κL in TlAgSe. The electronic origin of soft and anharmonic lattice is the presence of filled antibonding states in the valence band near the Fermi level constructed by Ag(4d)−Se(4p) and Tl(6s)−Se(4p) interactions. This work demonstrates that the evidence of dynamic distortion in a crystal lattice is governed by the third empirical rule given by Pauling, which can act as a potential new strategy for diminishing κL in crystalline solids. [ABSTRACT FROM AUTHOR]

Intrinsically low lattice thermal conductivity (κlat) while maintaining the high carrier mobility (μ) is of the utmost importance for thermoelectrics. Topological insulators (TI) can possess high μ due to the metallic surface states. TIs with heavy constituents and layered structure can give rise to high anharmonicity and are expected to show low κlat. Here, we demonstrate that Bi1.1Sb0.9Te2S (BSTS), which is a 3D bulk TI, exhibits ultra‐low κlat of 0.46 Wm−1 K−1 along with high μ of ≈401 cm2 V−1 s−1. Sound velocity measurements and theoretical calculations suggest that chemical bonding hierarchy and high anharmonicity play a crucial role behind such ultra‐low κlat. BSTS possesses low energy optical phonons which strongly couple with the heat carrying acoustic phonons leading to ultra‐low κlat. Further, Cl has been doped at the S site of BSTS which increases the electron concentration and reduces the κlat resulting in a promising n‐type thermoelectric figure of merit (zT) of ≈0.6 at 573 K. [ABSTRACT FROM AUTHOR]

BiTe, a member of the (Bi2)m(Bi2Te3)n homologous series, possesses natural van der Waals-like heterostructure with a Bi2 bilayer sandwiched between the two [Te-Bi-Te-Bi-Te] quintuple layers. BiTe exhibits both the quantum states of weak topological and topological crystalline insulators, making it a dual topological insulator and a suitable candidate for spintronics, quantum computing and thermoelectrics. Herein, we demonstrate that the chemical bonding in BiTe is to be metavalent, which plays a significant role in the pressure dependent change in the topology of the electronic structure Fermi surface. The enhancement of the metavalent bonding character with pressure in BiTe is evidenced from first-principles density functional theory (DFT) calculations. Due to the change in the Fermi surface topology, we have visualized electronic topological transitions (ETT) at 1 and 3 GPa through pressure dependent synchrotron X-ray diffraction analysis and Raman spectroscopy. The correlation between the metavalent bonding and ETT offers insights into chemical bonding influenced transitions in quantum materials., (© 2025 Wiley‐VCH GmbH.)

Modern technology demands miniaturization of electronic components to build small, light, and portable devices. Hence, discovery and synthesis of new non-toxic, low cost, ultra-thin ferroelectric materials having potential applications in various electronic and optoelectronic devices are of paramount importance. However, achieving room-temperature ferroelectricity in two dimensional (2D) ultra-thin systems remains a major challenge as conventional three-dimensional ferroelectric materials lose their ferroelectricity when the thickness is brought down below a critical value owing to the depolarization field. Herein, we report room-temperature ferroelectricity in ultra-thin single-crystalline 2D nanosheets of Bi 2 O 2 S synthesized by a simple, rapid, and scalable solution-based soft chemistry method. The ferroelectric ground state of Bi 2 O 2 S nanosheets is confirmed by temperature-dependent dielectric measurements as well as piezoelectric force microscopy and spectroscopy. High resolution transmission electron microscopy analysis and density functional theory-based calculations suggest that the ferroelectricity in Bi 2 O 2 S nanosheets arises due to the local distortion of Bi 2 O 2 layers, which destroys the local inversion symmetry of Bi 2 O 2 S., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)