n $Yields$ $pi$* ELECTRONIC TRANSITION IN PURE ALKALI NITRATE MELTS
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)
- Research Organization:
- Oak Ridge National Lab., Tenn.
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-15-015518
- OSTI ID:
- 4053844
- Journal Information:
- Journal of Chemical Physics (U.S.), Vol. Vol: 34; Other Information: Orig. Receipt Date: 31-DEC-61
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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