Reactivity of lanthanoid mono-cations with ammonia: A combined inductively coupled plasma mass spectrometry and computational investigation

Alexandre Quemet, Pierre Vitorge, Alvaro Cimas, Shengsi Liu, Jean Yves Salpin, Colin Marsden, Jeanine Tortajada, Laura Gagliardi, Riccardo Spezia, Marie Pierre Gaigeot, René Brennetot

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

The behavior of La+, Sm+, Eu+ and Gd + with NH3(g) and ND3(g) was studied to understand gas phase chemical reactions used for separations in the reaction cell of a quadrupole inductively coupled plasma-mass spectrometer (ICP-MS). For Ln+ = La+ and Gd+, the primary reaction channel is the formation of the LnNH+ protonated nitride leading to H 2 elimination. The LnNH(NH3)1-5+ ammonia complexes of the Ln protonated nitride are further generated. Sm + and Eu+ are less reactive: the protonated nitride is not detected, and only small amounts of Ln(NH3)0-6 + are observed. Quantum chemical calculations at the DFT, MP2, CCSD(T) and CASPT2 levels of theory were employed to explore the potential energy surfaces. For the La+ and Gd+ ions of f-block elements, the reaction pathways are composed of three steps: first the formation of LnNH3+, then the isomerization to HLnNH 2+, and finally the loss of H2 associated with the formation of an LnN triple bond in the final product LnNH+. On the other hand, the isomerization leading to triple bond formation with H 2 loss did not proceed for Sm+ and Eu+ ions.

Original languageEnglish (US)
Pages (from-to)27-37
Number of pages11
JournalInternational Journal of Mass Spectrometry
Volume334
DOIs
StatePublished - Jan 15 2013

Keywords

  • Ab initio
  • DFT
  • ICP-MS
  • Insertion reaction
  • Ion-molecule reactions
  • Lanthanides

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