Theoretical studies of potential energy surface and rotational spectra of Xe–H2O van der Waals complex

Abstract

In this work we report an ab initio intermolecular potential energy surface and theoretical spectroscopic studies for Xe-H(2)O complex. The ab initio energies are calculated with CCSD(T) method and large basis sets (aug-cc-pVQZ for H and O and aug-cc-pVQZ-PP for Xe) augmented by a {3s3p2d2f1g} set of bond functions. This potential energy surface has a global minimum corresponding to a planar and nearly linear hydrogen bonded configuration with a well depth of 192.5 cm(-1) at intermolecular distance of 4.0 A, which is consistent with the previous determined potential by Wen and Jager [J. Phys. Chem. A 110, 7560 (2006)]. The bound state calculations have been performed for the complex by approximating the water molecule as a rigid rotor. The theoretical rotational transition frequencies, isotopic shifts, nuclear quadrupole coupling constants, and structure parameters are in good agreement with the experimental observed values. The wavefunctions are analyzed to understand the dynamics of the ground and the first excited states.