Issue 17, 2024

Tunneling splittings in the vibrationally excited states of water trimer

Abstract

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 (D2O)3 are found to be two orders of magnitude smaller than in (H2O)3. Geometrical arguments were used to explain the order of states in some TS multiplets in vibrationally excited water trimers.

Graphical abstract: Tunneling splittings in the vibrationally excited states of water trimer

Article information

Article type
Paper
Submitted
02 Jan 2024
Accepted
01 Apr 2024
First published
01 Apr 2024

Phys. Chem. Chem. Phys., 2024,26, 12965-12981

Tunneling splittings in the vibrationally excited states of water trimer

M. Eraković and M. T. Cvitaš, Phys. Chem. Chem. Phys., 2024, 26, 12965 DOI: 10.1039/D4CP00013G

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