Thermal Properties of the Element and Binary Oxides toward Negative Thermal Expansion: A First-Principles Lattice-Dynamics Study

To establish the design principles of thermal properties of solids, we performed comprehensive calculations of volume thermal expansion coefficients αV, bulk moduli BT, average atomic volumes V, and Grüneisen parameters γ in the finite temperature for the 46 elements and 45 binary oxides using first-principles lattice-dynamics calculations. We clarified that (i) a crystal possessing large V tends to have small BT; (ii) the major role of γ is the determination of the sign of αV, the value of which is ruled by the crystal structures and coordination numbers; (iii) the transverse-acoustic (TA) and/or low-frequency phonons are responsible for the negative thermal expansion (NTE) behaviors; (iv) the NTE materials prefer the relatively large V with the void space, possessing negative mode-Grüneisen parameters γqν; and (v) the common feature of the NTE materials is the phonons vibrating forward to the void space. Our study provides a wide perspective on designing low and/or negative thermal expansion materials.