Gas-phase chemistry of nitrogen trifluoride NF3: structure and stability of its M+-NF3 (M = H, Li, Na, K) complexes

Abstract The stationary points characterizing the potential energy profiles of the complex processes of the M + (M=H, Li, Na, K) and NF 3 were investigated by QCISD and B3LYP in conjunction with the 6-311+G(2d,2p) basis set. The optimized geometries and NBO analysis indicate that the complexes of M + (M=Li, Na, K) and NF 3 exist as ion-dipole molecules. But for H + complexes, there are two stable isomers NF 3 H + and NF 2 + –HF. The interaction distances of isomers follow the sequence H + + + + . The calculated affinity energies of the most stable isomers of H + , Li + , Na + , and K + complexes exceed 20.1 kJ/mol, and these values suggest that the M + –NF 3 (M=H, Li, Na, K) complexes could be observed as stable species in gas phase, which supports Fujii's proposal that Li + ion attachment mass spectrometry can serve as a conceivable technique to quantify the emissions of the NF 3 .