Visible and near-infrared excitation spectra from the neptunyl ion doped into a uranyl tetrachloride lattice
Abstract
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-.
- Authors:
-
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1457255
- Alternate Identifier(s):
- OSTI ID: 1396701
- Report Number(s):
- LA-UR-15-26413
Journal ID: ISSN 0022-2860
- Grant/Contract Number:
- AC52-06NA25396
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Molecular Structure
- Additional Journal Information:
- Journal Volume: 1108; Journal Issue: C; Journal ID: ISSN 0022-2860
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Actinide; Electronic structure; Excitation spectrum; Intra-5f; Ligand-to-metal charge-transfer; Neptunyl
Citation Formats
Barker, Beau J., Berg, John M., Kozimor, Stosh A., Wozniak, Nicholas R., and Wilkerson, Marianne Perry. Visible and near-infrared excitation spectra from the neptunyl ion doped into a uranyl tetrachloride lattice. United States: N. p., 2015.
Web. doi:10.1016/j.molstruc.2015.12.027.
Barker, Beau J., Berg, John M., Kozimor, Stosh A., Wozniak, Nicholas R., & Wilkerson, Marianne Perry. Visible and near-infrared excitation spectra from the neptunyl ion doped into a uranyl tetrachloride lattice. United States. https://doi.org/10.1016/j.molstruc.2015.12.027
Barker, Beau J., Berg, John M., Kozimor, Stosh A., Wozniak, Nicholas R., and Wilkerson, Marianne Perry. Tue .
"Visible and near-infrared excitation spectra from the neptunyl ion doped into a uranyl tetrachloride lattice". United States. https://doi.org/10.1016/j.molstruc.2015.12.027. https://www.osti.gov/servlets/purl/1457255.
@article{osti_1457255,
title = {Visible and near-infrared excitation spectra from the neptunyl ion doped into a uranyl tetrachloride lattice},
author = {Barker, Beau J. and Berg, John M. and Kozimor, Stosh A. and Wozniak, Nicholas R. and Wilkerson, Marianne Perry},
abstractNote = {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-.},
doi = {10.1016/j.molstruc.2015.12.027},
journal = {Journal of Molecular Structure},
number = C,
volume = 1108,
place = {United States},
year = {Tue Dec 15 00:00:00 EST 2015},
month = {Tue Dec 15 00:00:00 EST 2015}
}
Web of Science