State-selective spectroscopy of water up to its first dissociation limit

Maxim Grechko, Oleg V. Boyarkin, Thomas R. Rizzo, Pavlo Maksyutenko, Nikolay F. Zobov, Sergei V. Shirin, Lorenzo Lodi, Jonathan Tennyson, Attila G. Császár, Oleg L. Polyansky

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46 Citations (Scopus)


A joint experimental and first-principles quantum chemical study of the vibration-rotation states of the water molecule up to its first dissociation limit is presented. Triple-resonance, quantum state-selective spectroscopy is used to probe the entire ladder of water's stretching vibrations up to 19 quanta of OH stretch, the last stretching state below dissociation. A new ground state potential energy surface of water is calculated using a large basis set and an all-electron, multireference configuration interaction procedure, which is augmented by relativistic corrections and fitted to a flexible functional form appropriate for a dissociating system. Variational nuclear motion calculations on this surface are used to give vibrational assignments. A total of 44 new vibrational states and 366 rotation-vibration energy levels are characterized; these span the region from 35 508 to 41 126 cm-1 above the vibrational ground state.

Original languageEnglish
Article number221105
JournalJournal of Chemical Physics
Issue number22
Publication statusPublished - Dec 28 2009

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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    Grechko, M., Boyarkin, O. V., Rizzo, T. R., Maksyutenko, P., Zobov, N. F., Shirin, S. V., Lodi, L., Tennyson, J., Császár, A. G., & Polyansky, O. L. (2009). State-selective spectroscopy of water up to its first dissociation limit. Journal of Chemical Physics, 131(22), [221105].