On the nature of [Fe 3 (CO) 12 ] in the solid-state: The Ligand Polyhedral Model approach to the observed disorder

Best Practices and Protocols in Mössbauer Spectroscopy

“…Finally, possibly for the same time-scale reason, the 4.2 to 295 K Mössbauer spectra reveal no evidence for either the D 3 or the D 3 h “half-way house” for the interconversion of the two C 2 v Fe 3 (CO) 12 molecules to form the “Star of David” average disordered Fe 3 (CO) 12 structure as has been proposed by Johnson and his co-workers, − who use the rather controversial ligand polyhedral model, LPM, to explain the dynamics of the formation of the disordered structure of Fe 3 (CO) 12 .…”

“…Both functionals, B3LYP and BP86, lead to the Fe 3 (CO) 12 ground state structure with the first D 3 h structure at 25.28 or 42.85 kJ/mol above the ground state, and with the second D 3 h structure at 36.61 or 36.28 kJ/mol above the ground state, respectively. Unfortunately, the authors do not report any calculations for the “Star of David” disordered structure of Fe 3 (CO) 12 nor for the hypothetical D 3 transition state suggested by Johnson for the Fe 3 (CO) 12 interconversion discussed above. The increasing energy ordering of the three structures is in agreement with that proposed by Johnson.…”