Tunneling splittings in the vibrationally excited states of water trimer.

Tunneling splitting (TS) patterns in vibrationally excited states of the water trimer are calculated, taking into account six tunneling pathways that describe the flips of free OH bonds and five bifurcation mechanisms that break and reform hydrogen bonds in the trimer ring. A tunneling matrix (TM) model is used to derive the energy shifts due to tunneling in terms of the six distinct TM elements in symbolic form. TM elements are calculated using the recently-developed modified WKB (Wentzel-Kramers-Brillouin) method in full dimensionality. Convergence was achieved for the lowest six excited vibrational modes. Bifurcation widths of the pseudorotational quartets are shown to be of comparable size to the ground-state widths, obtained using instanton theory, or increased for some particular modes of vibration. The largest increase is obtained for the excited out-of-phase flip of two adjacent water monomers with free OH bonds pointing in opposite directions relative to the ring plane. Bifurcation widths in (D 2 O) 3 are found to be two orders of magnitude smaller than in (H 2 O) 3 . Geometrical arguments were used to explain the order of states in some TS multiplets in vibrationally excited water trimers.