Theoretical investigation of rare gas hydride cations: HRgN2+ (Rg=He, Ar, Kr, and Xe)

Abstract

Rare gas containing protonated nitrogen cations, HRgN(2)(+) (Rg=He, Ar, Kr, and Xe), have been predicted using quantum computational methods. HRgN(2)(+) ions exhibit linear structure (C(∞v) symmetry) at the minima and show planar structure (C(s) symmetry) at the transition state. The stability is determined by computing the energy differences between the predicted ions and its various unimolecular dissociation products. Analysis of energy diagram indicates that HXeN(2)(+) is thermodynamically stable with respect to dissociated products while HHeN(2)(+), HArN(2)(+), and HKrN(2)(+) ions are metastable with small barrier heights. Moreover, the computed intrinsic reaction coordinate analysis also confirms that the minima and the 2-body global dissociation products are connected through transition states for the metastable ions. The coupled-cluster theory computed dissociation energies corresponding to the 2-body dissociation (HN(2)(+) + Rg) is -288.4, -98.3, -21.5, and 41.4 kJ mol(-1) for HHeN(2)(+), HArN(2)(+), HKrN(2)(+), and HXeN(2)(+) ions, respectively. The dissociation energies are positive for all the other channels implying that the predicted ions are stable with respect to other 2- and 3-body dissociation channels. Atoms-in-molecules analysis indicates that predicted ions may be best described as HRg(+)N(2). It should be noted that the energetic of HXeN(2)(+) ion is comparable to that of the experimentally observed stable mixed cations, viz. (RgHRg')(+). Therefore, it may be possible to prepare and characterize HXeN(2)(+) ions in an electron bombardment matrix isolation technique.

Theoretical investigation of HNgNH3+ ions (Ng = He, Ne, Ar, Kr, and Xe)

“…(The energy barriers for decomposition into NH 4 + and Ne are calculated to be 4.9 and less than 1 kJ mol −1 at the B3LYP and MP2 levels of theory, respectively.) For the He-, Ar-, Kr-, and Xe-derivatives, the HNgNH 3 + cation is higher in energy than the global minimum of NH 84 the energy barriers for the reaction HNgN 2 + → HN 2 + + Ng were calculated to be 2.3(6.2), 6.3(7.3), and 8.0(8.9) for Ng = He, Ar, and Kr at the B3LYP (CCSD(T)) levels of theory, respectively. Clearly, the HNgNH 3 + species possesses a higher stability than HNgN 2 + .…”

“…Phys. 142, 144301 ( 84 These values indicate relatively intense stretching vibrations of HNgNH 3 + (Ng = He, Ar, Kr, and Xe), which correspond to the chemical bonding species rather than weak van der Waals (vdW) complexes. .…”

“…. 84 The Mulliken charge analysis suggests that the H ′ NgNH 3 + cation may be appropriately described as [H ′ Ng] + -NH 3 , which is similar to H ′ NgN 2 + ions (Ng = He, Ar, Kr, and Xe).…”

“…83 Most recently, the stabilities of HNgN 2 + (Ng = He, Ar, Kr, and Xe) were theoretically investigated by Jayasekharan and Ghanty. 84 In this paper, we report the structures, energetics, and bonding properties of the title species HNgNH 3 + (Ng = He, Ne, Ar, Kr, and Xe). The high stability of these compounds is theoretically demonstrated by comparison with the experimentally prepared cations NgHNg +23, 24 and HNg +26-29 and the theoretically predicted HNgN 2 + ions.…”

On the vibrational linear and nonlinear optical properties of compounds involving noble gas atoms: HXeOXeH, HXeOXeF, and FXeOXeF

“…Apart from the synthesis and identification of rare gas compounds, a number of theoretical groups have reported studies on the stability, formation mechanisms, structure, and bonding nature of several rare gas compounds. [5,6,[25][26][27][28][29][30][31][32][33][34][35] We have reported that insertion of an Ng atom remarkably enhances the nonlinear response of the resulting derivative. [36] This has been attributed to the noteworthy lowering of the excited states accompanied by more intense allowed electronic transitions.…”