ELECTRONIC-STRUCTURE OF MIXED-VALENCE IONS - ESCA AND MO CALCULATIONS ON [ETA-5-C5H5FE(CO)]2-MU-PH2P(CH2)NPPH2M+ (N = 1, 2 - M = 0, 1)
Academic Article
Overview
Identity
Additional Document Info
Other
View All
Overview
abstract
The ESCA spectra of the title compounds are presented and compared to the results of parameter-free Fenske-Hall molecular orbital calculations. The calculations are used both to calculate ESCA satellite intensities via the sudden approximation and to describe the valence electronic structure. The results of the sudden approximation, which predict no satellites of intensity greater than 10% of the main peak, are in good agreement with the ESCA spectra, where no satellites are discernible. However, using the same theoretical results, we find that the Hush model predicts a single intense satellite, which is in disagreement with the full MO sudden approximation and the ESCA spectra. The description of the valence electronic structure is in good agreement with previous results for the cyclic voltammetry, for the carbonyl stretching frequencies, and for the crystal structures. However, they suggest that oxidation of the neutral species involves removal of an Fe-Fe nonbonding electron rather than removal of an electron from the Fe-Fe a bond. 1978, American Chemical Society. All rights reserved.
