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

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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► Reactivity of lanthanoid mono-cations with ammonia by Q-ICP-MS.
► Determination of potential energy surfaces by quantum chemical calculations.
► Different levels of theory (DFT, MP2, CCSD(T) and CASPT2) was performed.