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Vibrationally state selective overtone spectroscopy and state- and nuclear spin-dependent predissociation dynamics of weakly bound ortho- and para-Ne-HO complexes (D = 34.66 cm and D = 31.67 cm) are reported, based on near-infrared excitation of van der Waals cluster bands correlating with v = 2 ← 0 overtone transitions (|02〉 and |02〉) out of the ortho (1) and para (0) internal rotor states of the HO moiety. Quantum theoretical calculations for nuclear motion on a high level potential energy surface [CCSD(T)/VnZf12 (n = 3, 4)], corrected for basis set superposition error and extrapolated to the complete basis set (CBS) limit, are employed to successfully predict and assign Π-Σ, Σ-Σ, and Σ-Π infrared bands in the spectra, where Σ or Π represent approximate projections of the body-fixed HO angular momentum along the Ne-HO internuclear axis. IR-UV pump-probe experimental capabilities permit real-time measurements of the vibrational predissociation dynamics, which indicate facile intramolecular vibrational energy transfer from the HO v = 2 overtone vibrations into the VdWs (van der Waals) dissociation coordinate on the τ = 15-25 ns time scale. Whereas all predicted strong transitions in the ortho-Ne-HO complexes are readily detected and assigned, vibrationally mediated photolysis spectra for the corresponding para-Ne-HO bands are surprisingly absent despite ab initio predictions of Q-branch intensities with S/N > 20-40. Such behavior signals the presence of highly selective nuclear spin ortho-para predissociation dynamics in the upper state, for which we offer a simple mechanism based on Ne-atom mediated intramolecular vibrational relaxation in the HO subunit (i.e., |02〉 → {|01〉; v = 2}), which is confirmed by the ab initio energy level predictions and the nascent OH rotational (N), spin orbit (Π,), and lambda doublet product distributions.

Nuclear spin/parity dependent spectroscopy and predissociation dynamics in vOH = 2 ← 0 overtone excited Ne–H2O clusters: Theory and experiment