Magnetic and Orbital Orders Coupled to Negative Thermal Expansion in   Mott Insulators, Ca2Ru1-xMxO4 (M = Mn and Fe)
  Ca2RuO4 is a structurally-driven Mott insulator with a metal-insulator transition at TMI = 357K, followed by a well-separated antiferromagnetic order at TN = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts TMI by weakening the orthorhombic distortion and induces either metamagnetism or magnetization reversal below TN. Moreover, M doping for Ru produces negative thermal expansion in Ca2Ru1-xMxO4 (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio, {\Delta}V/V, reaching as high as 1%. The onset of the negative thermal expansion closely tracks TMI and TN, sharply contrasting classic negative thermal expansion that shows no relevance to electronic properties. In addition, the observed negative thermal expansion occurs near room temperature and extends over a wide temperature interval up to 300 K. These findings underscores new physics driven by a complex interplay between orbital, spin and lattice degrees of freedom. 
T. F. Qi, O. B. Korneta, S. Parkin, Jiangping Hu and G. Cao
cond-mat.str-el