DOE OSTI2017
Vibrationally state selective overtone spectroscopy and state- and nuclear spin-dependent predissociation dynamics of weakly bound ortho- and para-Ne–H 2 O 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 H 2 O 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 H 2 O angular momentum along the Ne–H 2 O 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 H 2 O v OH = 2 overtone vibrations into the VdWs (van der Waals) dissociation coordinate on the τprediss = 15-25 ns time scale. Whereas all predicted strong transitions in the ortho-Ne–H 2 O complexes are readily detected and assigned, vibrationally mediated photolysis spectra for the corresponding para-Ne–H 2 O 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 H 2 O subunit (i.e., |02 ± ⟩ → {|01 ± ⟩ v 2 = 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.
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