Calculated Effects of Disorder on the Mo Core Levels in Purple Bronze Li2Mo12O34

The band structures of ordered and thermally disordered Li2Mo12O34 are calculated by use of ab initio density functional theory (DFT)–Linear Muffin-Tin Method (LMTO) with a focus on the behavior of the Mo 3d -core levels. It is shown that thermal disorder and zero-point motion lead to substantial core level broadening, and the broadening at room temperature is predicted to be sufficiently larger than at zero degrees to allow for a detection by X-ray photoelectron spectroscopy (XPS) measurements. However, real purple bronze has 10% Li vacancies, and static disorder will attenuate the T-dependent broadening. It is argued that core level spectroscopies could be a useful tool for the measurement of thermal disorders in many materials, especially for those with minor static disorder. Studies of core levels in magnetic materials will be helpful for an understanding of T-dependent spin moments.