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 Πe/f(j = 1,k = 0) ← Σf(j = 0,k = 0) and Σf(j = 1,k = 0) ← Σf(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 Reff, force constant ks, and vdW stretching frequency νs. 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 Reff, ks, and νs with the polarizability of Rg in the ground and ν2 excited states. Anomalously small values of νs and ks derived for NH3-Xe in the Πe/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 Πf state. Such a state could not be found, however.