Nuclear spin/parity dependent spectroscopy and predissociation dynamics in v_OH = 2 ← 0 overtone excited Ne-H₂O...

Vibrationally state selective overtone spectroscopy and state- and nuclear spin-dependent predissociation dynamics of weakly bound ortho- and para-Ne-H₂O complexes (D_0(ortho) = 34.66 cm^-1 and D_0(para) = 31.67 cm^-1) are reported, based on near-infrared excitation of van der Waals cluster bands correlating with v_OH = 2 ← 0 overtone transitions (|02^-〉 and |02⁺〉) out of the ortho (1₀₁) and para (0₀₀) internal rotor states of the H₂O 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 H₂O angular momentum along the Ne-H₂O 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 H₂O v_OH = 2 overtone vibrations into the VdWs (van der Waals) dissociation coordinate on the τ_prediss = 15-25 ns time scale. Whereas all predicted strong transitions in the ortho-Ne-H₂O complexes are readily detected and assigned, vibrationally mediated photolysis spectra for the corresponding para-Ne-H₂O 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 H₂O subunit (i.e., |02^±〉 → {|01^±〉; v₂ = 2}), which is confirmed by the ab initio energy level predictions and the nascent OH rotational (N), spin orbit (Π_1/2,_3/2), and lambda doublet product distributions.