(Pb,Cd)-O covalency in PbTiO3-CdTiO3 with enhanced negative thermal expansion.

Recently experiments have found that negative thermal expansion is a common phenomenon in PbTiO3-based materials, and their negative thermal expansion is affected by various substitutions. Interestingly, Cd substitution in PbTiO3 has a unique effect in enhancing negative thermal expansion compared with any other A-site substitutions. Therefore, studying Cd substitution in PbTiO3, the role of which still remains unclear, would bring us deeper understanding on the nature of the negative thermal expansion of PbTiO3-based materials. Structure calculations, density of states, Bader analysis and the minimum electron density of Pb1-xCdxTiO3 supercells have been reported on the chemical bond through first-principles calculations here. We found that the hybridization between (Pb,Cd)-O orbitals exists in tetragonal phase. Furthermore, the hybridization between Cd-O orbitals is stronger than that between Pb-O orbitals, and Cd-O covalency promotes the average A-site hybridization. Simultaneously, the average bulk coefficient of thermal expansion is negative and inversely proportional to the Cd substitution amount. So, (Pb,Cd)-O covalency in the tetragonal Pb1-xCdxTiO3 is responsible for the nature of enhanced negative thermal expansion in accordance with our previous experimental investigations.