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.
Bibliographical noteFunding Information:
The contribution of LG and SL was supported by the Director, Office of Basic Energy Sciences, U.S. Department of Energy , under Contract USDOE/DE-SC002183 and the University of Minnesota Super-computing Institute .
- Ab initio
- Insertion reaction
- Ion-molecule reactions