Intermolecular dynamics of NH3-rare gas complexes in the ν2 umbrella region of NH3 investigated by rovibrational laser jet-cooled spectroscopy and ab initio calculations.

High resolution jet-cooled spectroscopy experiments have been realized to investigate the intermolecular dynamics of van der Waals (vdW) heterodimers between NH₃ and rare gas (Rg) atoms in the ν₂ umbrella mode region of NH₃. With respect to a previous study dedicated to NH₃-Ar [Asselin et al. Mol. Phys. 116, 3642 (2018)], the sensitivity and spectral resolution of our laser spectrometer coupled to a pulsed supersonic jet have been significantly improved to derive more accurate excited state spectroscopic parameters from rovibrational analyses. In addition, we calculated the ground and ν₂ excited vibration–rotation–tunneling (VRT) states of these complexes on the four-dimensional ab initio potential energy surfaces from Loreau et al. [J. Chem. Phys. 141, 224303 (2014), ibid. 143, 184303 (2015).] Transition frequencies and intensities of the allowed ν₂ = 1 ← 0 transitions obtained from the calculated energy levels and wave functions agree well with the experimental data and are helpful in their analysis. By means of a pseudodiatomic model with the assumption of weak Coriolis coupling, the rovibrational analysis of both the Π_e/f(j = 1,k = 0) ← Σ_f(j = 0,k = 0) and Σ_f(j = 1,k = 0) ← Σ_f(j = 0,k = 0) transitions in ortho NH₃-Rg (Rg = Ne, Ar, Kr, Xe) complexes enabled us to determine reliable excited state parameters and derive accurate values of the effective vdW bond length R_eff, force constant k_s, and vdW stretching frequency ν_s. Comparison between the experimental structural parameters and those from the ab initio calculated VRT levels shows good agreement for NH₃–Ne, NH₃–Ar and NH₃–Kr, and a similar variation of R_eff, k_s, and ν_s with the polarizability of Rg in the ground and ν₂ excited states. Anomalously small values of ν_s and k_s derived for NH₃-Xe in the Π_e/f(j = 1,k = 0) state suggest that the applied model is not valid in this case, due to the presence of another state coupling to the perturbed Π_f state. Such a state could not be found, however. [ABSTRACT FROM AUTHOR]