Nontrivial Spin Dimer in the Hexagonal Ruthenate Ba3CaRu2O9 Revealed by Nonmagnetic Ion Substitution

We have prepared a set of polycrystalline samples of Ba3Ca(Ru1−xNbx)2O9 consisting of the face-shared (Ru,Nb)2O9 dimer block from x = 0 to 0.12, and have measured the x-ray diffraction and magnetization. We find that all the samples of x > 0 show Curie–Weiss-like susceptibility below 30 K with the Weiss temperature θNb of 2–7 K, which suggests that the Nb-substituted NbRuO9 dimer interacts the Ru2O9 dimers magnetically. We also find the NbRuO9 dimer effectively works as S = 1 in the dilution limit, which is also suggested by the first-principle calculation. The Ru2O9 dimer lattice is nontrivial in the sense that S = 1 moment in the NbRuO9 dimer is screened for large x without any magnetic long range order. A possible origin is discussed.