Compression of curium pyrrolidine-dithiocarbamate enhances covalency

Nature
Joseph M SperlingThomas E Albrecht-Schmitt

Abstract

Curium is unique in the actinide series because its half-filled 5f 7 shell has lower energy than other 5f n configurations, rendering it both redox-inactive and resistant to forming chemical bonds that engage the 5f shell1-3. This is even more pronounced in gadolinium, curium's lanthanide analogue, owing to the contraction of the 4f orbitals with respect to the 5f orbitals4. However, at high pressures metallic curium undergoes a transition from localized to itinerant 5f electrons5. This transition is accompanied by a crystal structure dictated by the magnetic interactions between curium atoms5,6. Therefore, the question arises of whether the frontier metal orbitals in curium(III)-ligand interactions can also be modified by applying pressure, and thus be induced to form metal-ligand bonds with a degree of covalency. Here we report experimental and computational evidence for changes in the relative roles of the 5f/6d orbitals in curium-sulfur bonds in [Cm(pydtc)4]- (pydtc, pyrrolidinedithiocarbamate) at high pressures (up to 11 gigapascals). We compare these results to the spectra of [Nd(pydtc)4]- and of a Cm(III) mellitate that possesses only curium-oxygen bonds. Compared with the changes observed in the [Cm(pydtc)4]- spectra, w...Continue Reading

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Methods Mentioned

BETA
phosphorescence
X-ray

Software Mentioned

NLMO
SHELXTL
pDFT
OLEX2 GUI
ORCA
OpenMolcas
NBO6
Amsterdam DFT
MC
SQUEEZE

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