Open AccessState-selective spectroscopy of water up to its first dissociation limit
Author(s) -
Maxim Grechko,
Oleg V. Boyarkin,
Thomas R. Rizzo,
Pavlo Maksyutenko,
Н. Ф. Зобов,
Sergei V. Shirin,
Lorenzo Lodi,
Jonathan Tennyson,
Attila G. Császár,
O. L. Polyansky
Publication year - 2009
Publication title -
the journal of chemical physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.071
H-Index - 357
eISSN - 1089-7690
pISSN - 0021-9606
DOI - 10.1063/1.3273207
Subject(s) - dissociation (chemistry) , potential energy surface , atomic physics , ground state , chemistry , multireference configuration interaction , spectroscopy , vibration , basis set , potential energy , molecular vibration , bond dissociation energy , molecule , molecular physics , physics , quantum mechanics , organic chemistry
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.
Accelerating Research
Robert Robinson Avenue,
Oxford Science Park, Oxford
OX4 4GP, United Kingdom
Address
John Eccles HouseRobert Robinson Avenue,
Oxford Science Park, Oxford
OX4 4GP, United Kingdom