Infrared shifts of the water dimer from the fully flexible ab initio HBB2 potential

Abstract

We report calculations of the infrared shifts for the water dimer, as obtained from the recent ab initio fully flexible HBB2 potential of Bowman and co-workers. The rovibrational calculations, which formally are 12-dimensional plus overall rotation, were performed within the [6 + 6]d adiabatic separation which decouples the 'fast' intramolecular modes from the 'slow' intermolecular ones. Apart from this decoupling, each set of modes is treated in a fully variational approach. The intramolecular motion was described in terms of Radau coordinates, using the f-embedding formulation of Wei &Carrington, and neglecting the rovibrational Coriolis coupling terms. Within this adiabatic approximation, the intermolecular motion is handled in a similar way as for rigid monomers, except for the rotational constants B's, averaged over intramolecular modes that depend now on the intermolecular geometry. Comparison with experimental data shows an excellent overall agreement. © 2012 The Royal Society.