Visible and near-infrared excitation spectra from the neptunyl ion doped into a uranyl tetrachloride lattice
Journal Article
·
· Journal of Molecular Structure
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
We present that visible and near-infrared illumination induces 5f-5f and ligand-to-metal charge-transfer (LMCT) transitions of the neptunyl tetrachloride anion in polycrystalline Cs2U(Np)O2Cl4, and results in near-infrared luminescence from the second electronically excited state to the ground state. This photoluminescence is used as a detection method to collect excitation spectra throughout the near-infrared and visible regions. The excitation spectra of LMCT transitions in excitation spectra were identified in previous work. Here the measurement and analysis is extended to include both LMCT and intra-5f transitions. The results manifest variation in structural properties of the neptunium-oxo bond among the low-lying electronic states. Vibronic intensity patterns and energy spacings are used to compare bond lengths and vibrational frequencies in the excited states, confirming significant characteristic differences between those excited by 5f-5f transitions from those due to LMCT transitions. Lastly, results are compared with recently published RASPT2/SO calculations of [NpO2Cl4]2-.
- Research Organization:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Organization:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- Grant/Contract Number:
- AC52-06NA25396
- OSTI ID:
- 1457255
- Alternate ID(s):
- OSTI ID: 1396701
- Report Number(s):
- LA-UR--15-26413
- Journal Information:
- Journal of Molecular Structure, Journal Name: Journal of Molecular Structure Journal Issue: C Vol. 1108; ISSN 0022-2860
- Publisher:
- ElsevierCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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