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Author Smith, G. P. ♦ Boston, C. R.
Sponsorship USDOE
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
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)
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 1961-04-01
Publisher Department Oak Ridge National Lab., Tenn.
Journal Journal of Chemical Physics
Volume Number 34
Organization Oak Ridge National Lab., Tenn.


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