The Curious Case of Pu+: Insight on 5f Orbital Activity from Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) Reactions

Cox, Richard M.; Bubas, Amanda R.; Melby, Kali M.; French, Amanda D.; Rodriguez, Michael J.; Prange, Micah P.; Govind, Niranjan

doi:10.1021/acs.inorgchem.4c03263

Title: The Curious Case of Pu⁺: Insight on 5f Orbital Activity from Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) Reactions

Journal Article · 14 October 2024 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.4c03263 · OSTI ID:2475026

^[1]; Bubas, Amanda R. ^[1]; Melby, Kali M. ^[1];

^[1];

^[1]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

A comprehensive understanding of when and how 5f orbitals participate in complex chemical bonding is important for a variety of applications. The actinides are unique in that they possess 5f orbitals and can access high oxidation states, which make them attractive for use in catalysis. Fundamental studies of actinide–ligand interactions offer a mechanism to examine the activation of the 5f orbitals so that the selectivity of 5f orbitals can be assessed. A previous study examined the reaction of Pu⁺ + CO₂ and determined that the reaction efficiency is restricted by a barrier, namely, promotion from the Pu⁺ ground-state configuration, 5f⁶7s, to a reactive-state configuration, 5f⁵6d². Here, the present study illustrates the benefit of activation of Pu’s 5f orbitals when studying the reaction of Pu⁺ + NO. In this reaction, PuO⁺ forms in an exothermic, barrierless process. The 5f orbitals can and do participate in forming a linear intermediate, [N-Pu-O]⁺, and this drives the exothermic reaction. Understanding the conditions under which 5f orbitals are active in chemical bonding is the key to exploiting the actinides’ selective catalytic capabilities.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2475026

Report Number(s):: PNNL-SA--199527

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 43 Vol. 63; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: The Curious Case of Pu+: Insight on 5f Orbital Activity from Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) Reactions

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Title: The Curious Case of Pu⁺: Insight on 5f Orbital Activity from Inductively Coupled Plasma Tandem Mass Spectrometry (ICP-MS/MS) Reactions