Inelastic Neutron Spectra of Uranium Tetrafluoride Hydrate, UF4(H2O)(2.5)

Uranium tetrafluoride hydrate (UFH) is formed by immersing anhydrous UF4 under water for 12 h. UFH is therefore clearly a chemical species of environmental concern, as anhydrous UF4 is an intermediate uranium form in the nuclear fuel cycle. We use inelastic neutron scattering (INS) to probe the full vibrational spectra of UFH and its deuterated analogue in an effort to improve the fundamental understanding of its vibrational spectra. Coupled with density functional theory (DFT) calculations, the first for this compound, and full spectral modeling, we generate the complete vibrational spectra of UFH and compare them to prior optical spectroscopic results. In particular, the combination of DFT with INS allows us to identify multiple distinct chemical environments in the water bending and OH stretching regions. Whereas the water molecules directly bound to the U atoms execute OH stretching around 3600 cm(-1), a second class of H-bonded waters vibrate below 3000 cm(-1), an indicator of strong H bonding. In addition, a class of librational water modes are observed between 400 and 900 cm(-1), which themselves can be separated in energy according to their chemical environments. Measurements presented herein directly assist in the assignment of certain spectral features in the infrared spectrum and will inform future investigations of UFH for environmental or forensics purposes.