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.