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Doubly charged positive ions of chromium hexacarbonyl and molybdenum hexacarbonyl: Calculated and measured electronic‐state energies
Author(s) -
Harris F. M.,
Jackson P. J.,
Rontree J. A.,
Andrews S. R.,
Parry D. E.
Publication year - 1995
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1190300411
Subject(s) - chemistry , molybdenum , valence (chemistry) , ion , molecule , chromium , ionization energy , ionization , atomic physics , spectral line , ground state , electronic structure , spectroscopy , analytical chemistry (journal) , computational chemistry , inorganic chemistry , physics , organic chemistry , quantum mechanics , astronomy , chromatography
Double‐charge‐transfer spectroscopy was used to measure the double‐ionization energies of chromium hexacarbonyl and molybdenum hexacarbonyl molecules to triplet electronic states of the corresponding dications. The spectra were interpreted using data calculated using a modified MSXα method. The measured double‐ionization energy to the ground triplet state is 22.8 ± 0.5 eV for Cr(CO) 6 and 22.4 ± 0.5 eV for Mo(CO) 6 ; both values match, within experimental error, an earlier measurement of 22.8 ± 0.5 eV for W(CO) 6 . The spectra for the three hexacarbonyls are remarkably similar, probably reflecting that the electronic structures of the three molecules are almost identical in the valence region. The similarity is reflected in the calculated data; the Coulomb repulsions between the two positive holes which characterize the dictations' states are 4.54, 4.44 and 4.45 eV for Cr(CO) 6 2+ , Mo(CO) 6 2+and W(CO) 6 2+ , respectively. These values correspond to the repulsive energy for two single charges separated by just over 3 Å, this separation being consistent with the size of the molecules.