Tsay, Fun-Dow and Gray, Harry B. and Danon, J. (1971) Electron Paramagnetic Resonance and Optical Spectra of Pentacyanocobaltate(II). Journal of Chemical Physics, 54 (9). pp. 3760-3769. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:TSAjcp71
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Electron paramagnetic resonance (EPR) and optical spectral studies have been carried out on the pentacyanocobaltate(II) ion in ethylene glycol–water solutions, and in electron-irradiated powder samples of K3Co(CN)6. Both EPR and optical spectra observed for the ion in the powder samples are essentially similar to those obtained from the ethylene glycol–water solutions. There was no observable linewidth variation with nuclear spin states MI, no dependence on the different solvent media used, and no dependence on the concentration ratio Co2+/CN–, in both X-band and K-band spectra. The results indicate that the structure of Co(CN)<sub>5</sub><sup>3 - </sup> in solutions and in polycrystalline media is a slightly distorted square pyramid with no solvent bound in the sixth coordination site. The two strong hyperfine components with exceptionally large spacings occurring at the low-field end of the X-band spectrum are identified as the so-called angular anomalies. An effective method of simulation of the first-derivative EPR spectra of polycrystalline samples has also been developed.
|Additional Information:||©1971 American Institute of Physics. Received 26 August 1970. This research was supported by the U.S. Army Research Office, Durham. We thank Professor Sunney I. Chan for several helpful suggestions. We also acknowledge the assistance of Mr. George R. Rossman in performing the optical spectral studies. Arthur Amos Noyes Laboratory of Chemical Physics, Contribution No. 4121.|
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