title: Calculation of rotation-vibration energy levels of the water molecule with near-experimental accuracy based on an ab initio potential energy surface.
abstract: A recently computed, high-accuracy ab initio Born-Oppenheimer (BO) potential energy surface (PES) for the water molecule is combined with relativistic, adiabatic, quantum electrodynamics, and, crucially, nonadiabatic corrections. Calculations of ro-vibrational levels are presented for several water isotopologues and shown to have unprecedented accuracy. A purely ab initio calculation reproduces some 200 known band origins associated with seven isotopologues of water with a standard deviation (σ) of about 0.35 cm(-1). Introducing three semiempirical scaling parameters, two affecting the BO PES and one controlling nonadiabatic effects, reduces σ below 0.1 cm(-1). Introducing one further rotational nonadiabatic parameter gives σ better than 0.1 cm(-1) for all observed ro-vibrational energy levels up to J = 25. We conjecture that the energy levels of closed-shell molecules with roughly the same number of electrons as water, such as NH3, CH4, and H3O(+), could be calculated to this accuracy using an analogous procedure. This means that near-ab initio calculations are capable of predicting transition frequencies with an accuracy only about a factor of 5 worse than high resolution experiments.
authors.affiliation: Department of Physics and Astronomy, University College London , Gower Street, London WC1E 6BT, United Kingdom.
authors.forename: Oleg L
authors.initials: OL
authors.lastname: Polyansky
authors.forename: Roman I
authors.initials: RI
authors.lastname: Ovsyannikov
authors.forename: Aleksandra A
authors.initials: AA
authors.lastname: Kyuberis
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Lodi
authors.forename: Jonathan
authors.initials: J
authors.lastname: Tennyson
authors.forename: Nikolai F
authors.initials: NF
authors.lastname: Zobov