Reactivity of Lanthanoid Mono-Cations with Ammonia : a Combined Inductively Coupled Plasma Mass Spectrometry and Computational Investigation - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue International Journal of Mass Spectrometry Année : 2013

Reactivity of Lanthanoid Mono-Cations with Ammonia : a Combined Inductively Coupled Plasma Mass Spectrometry and Computational Investigation

Alvaro Cimas
Laura Gagliardi
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Résumé

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 H2 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 HLnNH2+, 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 H2 loss did not proceed for Sm+ and Eu+ ions.
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Dates et versions

hal-00796104 , version 1 (03-10-2018)

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Alexandre Quemet, Pierre Vitorge, Alvaro Cimas, Shengsi Liu, Jean-Yves Salpin, et al.. Reactivity of Lanthanoid Mono-Cations with Ammonia : a Combined Inductively Coupled Plasma Mass Spectrometry and Computational Investigation. International Journal of Mass Spectrometry, 2013, 334, pp.27-37. ⟨10.1016/j.ijms.2012.10.005⟩. ⟨hal-00796104⟩
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