title: State-selective spectroscopy of water up to its first dissociation limit.
abstract: 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.
authors.affiliation: Laboratoire de Chimie Physique Moléculaire (LCPM), Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland.
authors.forename: Maxim
authors.initials: M
authors.lastname: Grechko
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Boyarkin
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Rizzo
authors.forename: Pavlo
authors.initials: P
authors.lastname: Maksyutenko
authors.forename: Nikolay F
authors.initials: NF
authors.lastname: Zobov
authors.forename: Sergei V
authors.initials: SV
authors.lastname: Shirin
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Lodi
authors.forename: Jonathan
authors.initials: J
authors.lastname: Tennyson
authors.forename: Attila G
authors.initials: AG
authors.lastname: Császár
authors.forename: Oleg L
authors.initials: OL
authors.lastname: Polyansky