Prediction of metastable metal-rare gas fluorides:FMRgF ( M = Be and Mg; Rg = Ar , Kr and Xe)

The structure, stability, charge redistribution, bonding, and harmonic vibrational frequencies of rare gas containing group II-A fluorides with the general formula FMRgF (where M = Be and Mg; Rg = Ar , Kr, and Xe) have been investigated using second order Møller-Plesset perturbation theory, density functional theory, and coupled cluster theory [CCSD(T)] methods. The species, FMRgF show a quasilinear structure at the minima and a bent structure at the transition state. The predicted species are unstable with respect to the two-body dissociation channel, leading to the global minima ( M F 2 + Rg ) on the singlet potential energy surface. However, with respect to other two-body dissociation channel ( F M + Rg F ) , they are found to be stable and have high positive energies on the same surface. The computed binding energy for the two-body dissociation channels are 94.0, 164.7, and 199.7 kJ mol − 1 for FBeArF, FBeKrF, FBeXeF, respectively, at CCSD(T) method. The corresponding energy values are 83.4, 130.7, and 180.1 kJ mol − 1 for FMgArF, FMgKrF, and FMgXeF, respectively, at the same level of theory. With respect to the three-body dissociation ( F M + Rg + F ) channel as well as dissociation into atomic constituent, they are also found to be stable and have high positive energies. The dissociation of the predicted species typically proceeds via MRgF bending mode at the transition state. The computed barrier heights for the transition states are 11.4, 32.2, and 57.6 kJ mol − 1 for FBeArF, FBeKrF, and FBeXeF, respectively, at the CCSD(T) method. The corresponding barrier heights for the Mg containing species are 2.1, 9.2, and 32.1 kJ mol − 1 along the series Ar  Kr  Xe , respectively. The M  Rg bond energies of the FMRgF species is significantly higher than the corresponding bond energies of the M +  Rg species ( ∼ 53 and ∼ 15 kJ mol − 1 for Be +  Ar and Mg +  Ar , respectively). The computed energy diagram as well as the geometrical parameters along with the AIM results suggest that the species are metastable with partial covalent character in the M  Rg bonding. Thus, it may be possible to prepare and to characterize these species using low temperature matrix isolation technique.