Spectra of the D 2 O dimer in the O-D fundamental stretch region: Vibrational dependence of tunneling splittings and lifetimes.

The fundamental O-D stretch region (2600-2800 cm ^-1 ) of the fully deuterated water dimer (D ₂ O) ₂ is studied using a pulsed supersonic slit jet source and a tunable optical parametric oscillator source. Relatively high spectral resolution (0.002 cm ^-1 ) enables all six dimer tunneling components to be observed, in most cases, for the acceptor asymmetric O-D stretch, the donor free O-D stretch, and the donor bound O-D stretch vibrations. The dominant acceptor switching tunneling splittings are observed to decrease moderately in the excited O-D stretch states, to roughly 75% of their ground state values, whereas the smaller donor-acceptor interchange splittings show more dramatic and irregular decreases. Excited state predissociation lifetimes, as determined from the observed line broadening, show large variations (0.2 ≤ τ ≤ 5 ns) depending on the vibrational state, K-value, and tunneling symmetry. Another very weak band is tentatively assigned to a combination mode involving an intramolecular O-D stretch plus an intermolecular twist overtone. Asymmetric O-D stretch bands of the mixed isotopologue dimers D ₂ O-DOH and D ₂ O-HOD are also observed and analyzed.