A new ab initio intermolecular potential energy surface and predicted rotational spectra of the Kr-H2O complex.

We report a new three-dimensional ab initio intermolecular potential energy surface for the Kr-H(2)O complex with the H(2)O monomer fixed at its experimental averaged structure. Using the supermolecular approach, the intermolecular potential energies were evaluated at the coupled-cluster singles and doubles level with noniterative inclusion of connected triples with the full counterpoise correction for the basis set superposition error and a large basis set including bond functions. The global minimum corresponding to a planar H-bond configuration was located at the intermolecular distance of 3.82 Å with a well depth of 169.98 cm(-1). In addition, two first-order and one second-order saddle points were also identified. The combined radial discrete variable representation∕angular finite basis representation method and the Lanczos algorithm were employed to calculate the rovibrational energy levels for 16 isotopic species of the Kr-H(2)O complexes. The rotational transition frequencies, structure parameters, and nuclear quadrupole coupling constants were also determined for the ground and first intermolecular vibrational excited states and are all in good agreement with the available experimental values.