Optical spectra of the dibromide and diiodide ions in the matrix-isolated M/sup +/Br/sub 2//sup -/ and M/sup +/I/sub 2//sup -/ species. [M = Na, Li, or K; 17/sup 0/K]
Journal Article
·
· J. Am. Chem. Soc.; (United States)
The products of argon matrix reactions of alkali metal atoms and bromine and iodine have been studied optically in thin films on a sapphire window at 17/sup 0/K. The bromine reaction produced a strong band near 360 and a weak band near 640 nm, depending upon the alkali reagent, and the reactions with iodine gave a strong absorption near 380 and a medium intensity absorption near 680 nm. These bands are due to sigma ..-->.. sigma* and ..pi.. ..-->.. sigma* transitions, respectively, of the dihalide anions in the M/sup +/X/sub 2//sup -/ species. The small alkali metal effect on the transition energies is in accord with an ionic model of polarizable ion pairs, with the exception of cesium, which is capable of inner shell bonding and red-shifting the transitions from their expected positions. In addition, a very strong 227 nm absorption in bromine and a strong 254, 286 nm doublet in iodine experiments are attributed to molecular halogen aggregates. (auth)
- Research Organization:
- Univ. of California, Berkeley
- OSTI ID:
- 7279914
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 98:8; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
ALKALI METALS
ALUMINIUM COMPOUNDS
ALUMINIUM OXIDES
ARGON
BROMIDES
BROMINE COMPOUNDS
CESIUM BROMIDES
CESIUM COMPOUNDS
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CORUNDUM
DECOMPOSITION
DIMERS
ELEMENTS
ENERGY-LEVEL TRANSITIONS
HALIDES
HALOGEN COMPOUNDS
INTERMEDIATE STRUCTURE
IODIDES
IODINE COMPOUNDS
KINETICS
LITHIUM
MATRIX ELEMENTS
METALS
MINERALS
NONMETALS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
POTASSIUM
RARE GASES
REACTION KINETICS
SAPPHIRE
SODIUM
SPECTRA
ULTRAVIOLET SPECTRA
400201* -- Chemical & Physicochemical Properties
ALKALI METAL COMPOUNDS
ALKALI METALS
ALUMINIUM COMPOUNDS
ALUMINIUM OXIDES
ARGON
BROMIDES
BROMINE COMPOUNDS
CESIUM BROMIDES
CESIUM COMPOUNDS
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CORUNDUM
DECOMPOSITION
DIMERS
ELEMENTS
ENERGY-LEVEL TRANSITIONS
HALIDES
HALOGEN COMPOUNDS
INTERMEDIATE STRUCTURE
IODIDES
IODINE COMPOUNDS
KINETICS
LITHIUM
MATRIX ELEMENTS
METALS
MINERALS
NONMETALS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
POTASSIUM
RARE GASES
REACTION KINETICS
SAPPHIRE
SODIUM
SPECTRA
ULTRAVIOLET SPECTRA