Low-lying states and electronic spectroscopy of iron(II) prophine
Calculations are made on the low-lying electronic states of iron(II) porphine. Although these calculations yield the /sup 3/A/sub 2g/ state as lowest, an argument is presented in favor of the /sup 3/E/sub g/ state calculated to lie some 240 cm/sup -1/ higher in energy. A detailed discussion of these results in conjunction with various seemingly conflicting experimental and theoretical results is made. The UV visible spectra is computed assuming each of five possible ground states, /sup 1/A/sub 1g/, /sup 3/A/sub 2g/, /sup 3/E/sub g/, /sup 5/E/sub g, /sup 5/A/sub 1g/, and /sup 5/E/sub g/. The calculated spectra from the /sup 3/A/sub 2g/ and /sup 3/E/sub g/ states are in good accord with experiment, and we argue that the extra bands observed at 12,500 and 15,000 cm/sup -1/ are due to trip-triplets, porphyrin ..pi.. ..-->.. ..pi..* triplets that have gained intensity by spin coupling with the iron atom triplet state. The calculated charge-transfer and d ..-->.. d spectra are described and are compared with other calculations. Although d ..-->.. d states are predicted to lie below the Q band they are either spatially or spin forbidden and might be difficult to observe. We do not calculate any charge-transfer excitations below the Q band in contrast to the calculations of others.
- Research Organization:
- Univ. of Florida, Gainesville
- OSTI ID:
- 5455694
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 108:9
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRON COMPOUNDS
ENERGY LEVELS
PORPHYRINS
CALCULATION METHODS
COUPLING
ELECTRON TRANSFER
THEORETICAL DATA
CARBOXYLIC ACIDS
DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)