Mössbauer studies of after-effects of auger ionization following electron capture in cobalt complexe

Abstract

Abstract The electron-capture decay of a cobalt-57 atom triggers an Auger event resulting in the loss of several electrons from the molecule in which it is incorporated. The 14.4 keV Mössbauer emission conveys information regarding the chemical forms in which the daughter iron-57 is ‘stabilized’ within 10−7 sec following electron capture. During this time the electronic relaxation occurs completely and several tens of electron volt energy is deposited in the molecule as a result of neutralization. We find that the ethylenediamine tetra-acetate, bis-salicylaldehyde tri-ethylenetetramine, acetylacetone, and indenyl chelates fragment in a large majority of events, resulting in the formation of degraded ionic Fe2+ and Fe3+ in the former cases and C9H7Fe+ in the latter. On the other hand, highly conjugated compounds such as cobalt phthalocyanine and Vitamin B12 escape fragmentation in 100 per cent of the Auger events. Tris-dipyridyl Co(III) perchlorate also escapes fragmentation in a majority of events. Apparently, the large amount of excitation energy deposited in the molecule as a consequence of charge neutralization is very rapidly (in less than 10−13sec) and efficiently dispersed through neighboring molecules. It is a novel phenomenon. When the dipyridyl chelate molecules are dispersed in a foreign matrix, the dissipation of charge and energy is no longer rapid and efficient and the probability of fragmentation is considerably enhanced. We also find that part of the coordinated parent species, in the case of labeled dipyridyl chelate, arises through fragmentation followed by interaction of the electronically excited degraded iron species with a neighboring chelate molecule resulting in replacement of cobalt with an iron atom. This finding was made possible by using the chelate doped with ‘carrier-free’ 57Co citrate. Emission spectroscopy yields values for the isomer shifts and quadrupole splittings which differ somewhat from those obtained by absorption spectroscopy. The apparent disparities are attributed to the dissimilarities of the matrices in which the Mössbauer emitter or absorber is situated.