Microscopic Origin of Random Singlet Behavior in B-site Disordered Spin-1/2 Perovskite BaCu_1/3Nb_2/3O_3 Revealed by EXAFS and Thermodynamics

Abstract

We report a combined structural and thermodynamic study of the ABO$_3$-type disordered perovskite BaCu$_{1/3}$Nb$_{2/3}$O$_3$ (BCNO), whose B site is jointly occupied by Cu and Nb in the $1:2$ ratio. Using synchrotron powder x-ray diffraction (XRD) and x-ray absorption fine structure (XAFS) spectroscopy, we investigate the microscopic nature of Cu$^{2+}$/Nb$^{5+}$ disorder on the pseudo-cubic B-sublattice and its relation to the emergent random-singlet (RS) behavior evidenced at low temperatures. While XRD reveals no long-range Cu/Nb ordering and average site occupancy consistent with stoichiometry, XAFS reveals a peculiar local chemical order characterized by preferential heteroatomic Cu$:$Nb correlations. This local arrangement strongly suppresses direct Cu$:$Cu linkages, despite the Cu concentration being close to the percolation threshold of a cubic lattice. The resulting exchange network explains the absence of spin-glass freezing or long-range magnetic order in the presence of substantial antiferromagnetic interactions, as indicated by a Curie-Weiss temperature $\Theta_{CW}\approx -50$ K. Instead, the magnetic susceptibility $\chi(T)$ and specific heat $c_p(T)$ exhibit power-law behavior and characteristic single-parameter $T/H$ scaling over broad temperature and magnetic-field ranges, consistent with random-singlet phenomenology. Notably, at very low temperatures, the specific heat behavior transitions from $T^{1-\gamma}$ ($\gamma \approx 0.6$ from the $T/H$ scaling) in zero-field to a T-linear dependence under high field, indicating a crossover to a distinct low-energy regime whose microscopic origin remains to be established.