An adiabatic model for calculating overtone spectra of dimers such as (H(2)O)(2).

The near-infrared and visible wavelength spectrum of the water dimer is considered to be the major contributor to the so-called water continuum at these wavelengths. However, theoretical models of this spectrum require the simultaneous treatment of both monomer and dimer excitations. A model for treating this problem is proposed which is based upon a Franck-Condon-like separation between the monomer and dimer vibrational motions. In this model, one of the monomers is treated as the chromophore and its absorption is assumed to be given by its, possibly perturbed, vibrational band intensity. The main computational issue is the treatment of separate monomer and dimer motions. Various approaches for obtaining dimer vibration-rotation tunnelling spectra that allow for monomer motion are explored. These approaches include ways of treating the adiabatic separation of dimer vibrational modes from monomer vibrational modes. We classify the adiabatic separation methods under four main approaches: namely fixed-geometry, free-monomer, perturbed-monomer and coupled-monomer methods. The latter being the most computationally expensive as the monomer wave functions are dependent on the dimer coordinates. For each of these approaches, expectation values over the full potential are calculated for the given monomer vibrational wave functions. Various full (named VAP 2pD in the text) and partial (VAP (+p)D) averaging techniques are outlined to calculate the vibrationally averaged, monomer state-dependent, dimer interaction potentials. The computational costs associated with application of these techniques to the water dimer are estimated and the prospects for full calculations based on this approach are assessed.