Ca 2 MnO 4 structural path: Following the negative thermal expansion at the local scale
The oxygen octahedral rotations in Ca 2 MnO 4 , the first member of the CaO(CaMnO 3 )n Ruddlesden-Popper family, is probed through a set of complementary techniques, including temperature-dependent neutron and x-ray diffraction, combined with local probe studies and ab initio calculations. Here we demonstrate the enhancement of the uniaxial negative thermal expansion coefficient from -1.26 ± 0.25 to -21 ± 1.8 ppm/K at the second order I4 1 /acd to I4/mmm structural phase transition, providing direct evidence for the corkscrew atomic mechanism. We establish, also, that the predicted I4/mmm high symmetry is attained around 1050 K. At lower temperatures, within the 10–1000 K temperature range, our first-principles calculations and detailed analysis of the Ca local environment reveals that the reported Aba2 structural phase, coexisting with the I4 1 /acd one, cannot describe correctly this compound. On the other hand, our data allow for the coexistence of the locally identical I4 1 /acd and Acam structural phases.