Solid-state luminescence spectra of five crystalline platinum(II) complexes at variable pressure and temperature are presented and compared. Maxima occur between 14000 cm-1 and 15600 cm-1 (approximately 700 nm to 640 nm) at ambient temperature and pressure. Spectra can be broad bands, characteristic of MLCT transitions, or vibronically structured, characteristic of intraligand transitions. Both pressure and temperature variations can lead to distinctive changes in the luminescence spectra that differ between these two types of transitions. MLCT band maxima show shifts on the order of-20 cm-1 /kbar to lower energy; in contrast, ligand-centered luminescence bands do not show significant shifts between ambient pressure and 40 kbar.
A new nuclear forensic reference material has been characterized as a standard for radiochronometric determination of the model purification date for 137Cs sources. The purification date of a radioactive source is a potentially diagnostic nuclear forensic signature for determining the provenance of a radioactive material. Reference values have been measured for the attributes needed to use the 137Cs/137Ba chronometer: the molality (reported here as nmol g−1) of 137Cs and of the radiogenic portion of 137Ba in the material (hereafter referred to as 137Ba*). All measurement results were decay-corrected to represent the composition of the material on the reference date of July 7, 2011. The molality of 137Cs is (0.7915 ± 0.0073) nmol g−1; this value was calculated from the massic activity of 137Cs, (348.4 ± 3.0) kBq g−1, as measured in the NIST 4π-γ secondary standard ionization chamber (previously calibrated by 4π-(e+x)-γ-coincidence efficiency extrapolation counting) and the evaluated half-life of 137Cs, (30.05 ± 0.08) years. The molality of 137Ba*, (1.546 ± 0.024) nmol g−1, was measured by isotope dilution mass spectrometry using the measured relative proportion of 138Ba in the material to apply a correction for the 137Ba contribution from natural Ba. A model age of (47.04 ± 0.56) years, corresponding to a model purification date of June 22, 1964 with an expanded uncertainty of 200 days is calculated from the reference material values. This age is consistent with the date engraved on the capsule that contained the 137Cs starting material and with a prior independent determination of the model purification date. A full discussion of the uncertainties of the reference material values is included.
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