Induced quadrupolar singlet ground state of praseodymium in a modulated pyrochlore

Abstract

The complex structure and magnetism of Pr2−𝑥⁡Bi𝑥⁢Ru2⁢O7 was investigated by neutron scattering and extended x-ray absorption fine structure. Pr has an approximate doublet ground state and the first excited state is a singlet. While the 𝐵-site (Ru) is well ordered throughout, this is not the case for the 𝐴-site (Pr/Bi). A broadened distribution for the Pr-O2 bond length at low temperature indicates the Pr environment varies from site to site even for 𝑥=0. The environment about the Bi site is highly disordered ostensibly due to the 6⁢𝑠 lone pairs on Bi3+. Correspondingly, we find that the non-Kramers doublet ground-state degeneracy, otherwise anticipated for Pr in the pyrochlore structure, is lifted so as to produce a quadrupolar singlet ground state with a spatially varying energy gap. For 𝑥=0, below 𝑇𝑁, the Ru sublattice orders antiferromagnetically, with propagation vector 𝐤=(0,0,0) as for Y2⁢Ru2⁢O7. No ordering associated with the Pr sublattice is observed down to 100 mK. The low-energy magnetic response of Pr2−𝑥⁡Bi𝑥⁢Ru2⁢O7 features a broad spectrum of magnetic excitations associated with inhomogeneous splitting of the Pr quasidoublet ground state. For 𝑥=0 (𝑥=0.97), the spectrum is temperature dependent (independent). It appears disorder associated with Bi alloying enhances the inhomogeneous Pr crystal-field level splitting so that intersite interactions become irrelevant for 𝑥=0.97. The structural complexity for the 𝐴-site may be reflected in the hysteretic uniform magnetization of 𝐵-site ruthenium in the Néel phase.