title: A nine-dimensional calculation of the vibrational OH stretching and HOH bending spectrum of the water trimer.
abstract: We have studied the vibrational high-frequency spectrum of the water trimer computationally. We expand an earlier study [J. Chem. Phys. A 2009, 113, 9124-9132] where we approximated the water trimer as three individually vibrating water monomer units. Some intramolecular potential energy coupling terms are now included in the previous model. The six OH bond lengths and the three HOH bending angles are used as the internal coordinates. The kinetic energy operator is a sum of the kinetic energy operators of the monomer units. We use the coupled cluster method with single, double, and perturbative triple excitations method [CCSD(T)] with augmented correlation consistent polarized valence triple-ζ (aug-cc-pVTZ) basis set to calculate the potential energy surface (PES). The counterpoise correction is included in the one-dimensional part of the PES. We calculate the vibrational energy eigenvalues using the variational method. The corresponding eigenfunctions are used to obtain the absorption intensities.
authors.affiliation: Laboratory of Physical Chemistry, Department of Chemistry, A.I. Virtasen aukio 1 (P.O. BOX 55), FI-00014, University of Helsinki, Finland.
authors.forename: Teemu
authors.initials: T
authors.lastname: Salmi
authors.forename: Elina
authors.initials: E
authors.lastname: Sälli
authors.forename: Lauri
authors.initials: L
authors.lastname: Halonen