Application of Atomic Hirshfeld Surface Analysis to Intermetallic Systems: Is Mn in Cubic CeMnNi4 a Thermoelectric Rattler atom?

The Mn atom in the cubic polymorph of CeMnNi4 appears to be located in an oversized cage-like structure, and anomalously large atomic displacement parameters (ADPs) for the Mn atom indicate that it is a potential rattler atom. Here, multitemperature synchrotron powder X-ray diffraction data measured between 110 and 900 K are used to estimate ADPs for the Mn guest atom and the host structure atoms in cubic CeMnNi4. The ADPs are subsequently fitted with Debye and Einstein models, giving Theta(D) = 301(2) K for the host structure and Theta(E) = 165(2) K for the Mn atom. This is higher than typical Einstein temperatures for rattlers in thermoelectric skutterudites and clathrates (Theta(E) = 50-80 K), indicating that the Mn atom in cubic CeMnNi4 is more strongly bonded. In order to probe the chemical interactions of the potential Mn rattler atom, atomic Hirshfeld surface (AHS) analysis is carried out and compared with AHS analysis of well-established guest atom rattlers in archetypical skutterudites, MCoSb3. Surprisingly, the skutterudite rattlers have more deformed AHSs than the Mn atom in cubic CeMnNi4. This is related to the highly ionic nature of the skutterudite rattlers, which is not taken into account in the neutral spherical atom approach of the AHS. Additionally, visualization of void spaces in the two materials using the procrystal electron density shows that while the Mn atom is tightly fitting in the CeMnNi4 structure then the La atom in the skutterudite is truly situated in an oversized cage of the host structure. Overall, we conclude that the Mn atom in cubic CeMnNi4 cannot be coined a rattler.