Ultralow Lattice Thermal Conductivity Induced by Quasi-Chain Configuration in Rb2Se3

Abstract: Alkali metal-based compounds have garnered significant attention due to their exceptionally low lattice thermal conductivity, which is crucial for applications in thermoelectric energy conversion and thermal barrier coatings. However, the fundamental mechanisms underlying such ultralow lattice thermal conductivity remain poorly understood. In this study, we investigate the intrinsic origins of the ultralow lattice thermal conductivity in the alkali metal-based ionic compound Rb2Se3, which exhibits a simple orthorhombic structure. By employing first-principles density functional theory (DFT) and solving the phonon Boltzmann transport equation (BTE), we reveal that Rb2Se3 achieves lattice thermal conductivity values below 0.2 W/mK along all crystallographic directions at 300 K. Our analysis uncovers a unique quasi-chain configuration within the crystal structure, characterized by strongly covalent Se-Se-Se trimers that act as localized rigid units, while Rb atoms occupy weakly bonded interstitial sites. This configuration induces pronounced anisotropy, weak bonding, and strong anharmonicity, leading to significant rattling-like behavior of all atoms and a dominance of low-frequency phonon modes. The interplay between the rigid Se trimers and the soft Rb matrix results in extreme phonon anharmonicity, as evidenced by large Gruneisen parameters and high atomic displacement parameters (ADPs). These findings provide a comprehensive understanding of the low lattice thermal conductivity in Rb2Se3 and establish a universal framework for designing low lattice thermal conductivity materials through the combination of rigid covalent clusters and soft ionic sublattices.