title: Calculated band profiles of the OH-stretching transitions in water dimer.
abstract: We have calculated the band profiles of the OH-stretching fundamental and overtone transitions in the proton donor unit of the water dimer complex. We have used a local mode Hamiltonian that includes both OH-stretching and OO-stretching motion but separates these adiabatically. The variation of OH-stretching frequency and anharmonicity with OO displacement from equilibrium contributes to the effective OO-stretching potentials for each OH-stretching state. The resulting OO-stretching energy levels and wave functions are used to simulate the vibrational profile of each OH-stretching transition. The coupled cluster with singles, doubles, and perturbative triples ab initio method with an augmented triple-zeta correlation consistent basis set has been used to obtain the necessary parameters, potentials, and dipole moment functions. We find that the OO-stretching transitions associated with a given hydrogen bonded OH-stretching transition are spread significantly and this spread increases with overtone. The spread is minor for the free OH-stretching transition. The inclusion of the OO-stretching mode has a limited effect on the overall OH-stretching band intensity.
authors.affiliation: Department of Chemistry, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand.
authors.forename: Anna L
authors.initials: AL
authors.lastname: Garden
authors.forename: Lauri
authors.initials: L
authors.lastname: Halonen
authors.forename: Henrik G
authors.initials: HG
authors.lastname: Kjaergaard