|Author||Smith, G. P. ♦ Boston, C. R.|
|Source||United States Department of Energy Office of Scientific and Technical Information|
|Subject Keyword||CHEMISTRY ♦ ABSORPTION ♦ ALKALI METALS ♦ CESIUM NITRATES ♦ COMPUTERS ♦ ELECTRONICS ♦ ELECTRONS ♦ ENERGY LEVELS ♦ FRANCK-CONDON PRINCIPLE ♦ LITHIUM NITRATES ♦ MELTING ♦ NITRATES ♦ RUBIDIUM NITRATES ♦ TRANSIENTS ♦ TRANSITIONS|
|Abstract||The lowest-energy transition (n - pi *) of the nitrate ion was found to shift in energy and intensity in a systematic way over the series of molten alkali nitrates from LiNO/sub 3/ through CsNO/sub 3/. Tbe energy E of the band maximum varied in a linear way with the cationic radius. At 365 deg C (extrapolated for CsNO/sub 3/) E in electron volts was given by (3.81 + 0.33/r/ sub 0/), where r/sub 0/ is the cationic radius (Ahrens) in A. The temperature dependence dE/dT was of the order of -10/sup -4/ ev/deg and increased in magnitude with increasing cationic l/r/sub 0/. The f number (oscillator strength) decreased steadily along the series of alkali nitrates from-4.1 x 10/ sub -4/ for LiNO/sub 3/ down to 0.86 x 10/sup -4/ for RbNO/sub 3/ and then rose again to 1.0 x 10/sup -4/ for CsNO/sub 3/. The thermal coefficient (l/f) (df/dT) was in the range of 10/sup -4/ to 10/sup -3/ deg/sup -1/. The bandwidth changed b y only a small amount for changes either in cation or in temperature. The origin of the observed shifts was considered in terms of interionic cohesive forces by application of the Franck-Condon and conservation of energy principles to a localized transition in a classical ionic melt. Digital computer procedures for profile analysis were described whereby an absorption band may be separated from an overlapping absorption edge. (auth)|
|Learning Resource Type||Article|
|Publisher Department||Oak Ridge National Lab., Tenn.|
|Journal||Journal of Chemical Physics|
|Organization||Oak Ridge National Lab., Tenn.|
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