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Analysis of Partition Functions for Metallocenes: Ferrocene, Ruthenocene, and Osmocene.

We present a calculation of the torsional potential of the three metallocenes of the iron group, that is, ferrocene, ruthenocene, and osmocene, calculated with the GAUSSIAN program suite. Both a variational method (through computation of the exact energy levels) and our Chebyshev imaginary time propagation method are used to calculate the hindered rotation partition function, demonstrating the efficiency of the Chebyshev scheme. The transition from a semirigid through a hindered rotor to the free rotor regime is demonstrated, and the effect of the hindered rotation (as opposed to a harmonic) treatment on the thermodynamics of metallocenes is demonstrated.