Flexibility of oxygen sublattice and hydrogen bond length predict proton mobility in ternary metal oxides

Discovery of fast proton conductors is important for advancing clean energy technologies. This requires a better understanding of proton migration mechanisms. While structural and chemical traits of ternary metal oxides have been related to proton migration barriers, lattice dynamical effects have not been resolved quantitatively. Here, in this work, we introduce a phonon-based dynamic descriptor, termed ‘‘thermal O…O fluctuation,’’ quantifying the flexibility of donor-acceptor oxide-ion pairs. This enables direct comparison of O-sublattice flexibility across diverse metal oxides. Using regression models, we ranked physical descriptors as predictors of proton mobility, finding that H-bond length and thermal O…O fluctuation were the strongest descriptors. Further analysis revealed a critical O…O spacing of 2.4 A˚ at the transition state, which is easier to reach by more flexible donor-acceptor pairs, enabling facile proton transfer. Our results demonstrate oxygen sublattice flexibility as a dynamic descriptor and provide guiding principles for enhancing proton mobility in ternary metal oxides.. Authors: Chung, Heejung W. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)] (ORCID:0000000213005201); Žguns, Pjotrs [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Latvia, Riga (Latvia)]; Li, Ju [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)]; Yildiz, Bilge [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)] (ORCID:0000000226885666). DOE Contract: SC0023450. Subjects: diffusivity; hydrogen bond; ion mobility; lattice dynamics; lattice flexibility; phonons; physical descriptors; proton transport; solid oxides; ternary metal oxides