Local Lattice Distortion Caused by Short Range Charge Ordering in LiMn₂O₄

We have performed powder neutron diffraction on $^7$Li-enriched sample of LiMn$_2$O$_4$ at 300 K. The crystal structure determined by Rietveld analysis is a cubic spinel with space group of $Fd\bar{3}m$ in which all Mn atoms are crystallograghically equivalent, consistent with many preceding studies. However, the atomic pair distrubution function (PDF) of this compound can not be fitted by the cubic structure with space group of $Fd\bar{3}m$ satisfactorily, and it can be reproduced by the orthorhombic structure with $Fddd$. It corresponds with the structure of charge ordered phase below about 260 K, indicating a short range charge ordering. In the local structure determined by PDF analysis, two types of MnO$_6$ octahedra with long and short atomic distances between Mn and O atoms exist and their Mn-O distances are almost consistent with the distances in the charge ordered phase. From these results, valence electrons are localized at Mn sites like a glass even in the cubic phase, resulting in the non-metallic electrical conductivity.