The geometries in the staggered and eclipsed conformations of the metallocenes, M(C5H5)2 with M = Mn, Fe, Co, Ni, and Ru, have been calculated at the local and nonlocal density functional theory (LDFT and NLDFT) levels. The M-C distance is predicted to be too short at the LDFT level and too long at the NLDFT level. The doublet low-spin states for M = Mn and Co show distortions away from the idealized fivefold symmetries. The low-spin state for M = Mn is predicted to be lower in energy than the high-spin state in contrast to the observed experimental results. The size of the splitting is strongly dependent on the computational level. The values of a and ? were calculated for the various metallocenes. The highest value of ? was found for M = Co.
Revised: November 19, 2020 |
Published: December 1, 1997
Citation
Matsuzawa N., J. Seto, and D.A. Dixon. 1997.Density Functional Theory Predictions of Second-Order Hyperpolarizabilities of Metallocenes.Journal of Physical Chemistry A 101, no. 49:9391-9398. PNWD-SA-4484. doi:10.1021/jp952465v