Ab initio configuration interaction description of excitation energy transfer between closely packed molecules

We present new, generally applicable protocols for the computation of the coupling parameter, J, of excitation energy transfer with quantum chemical ab initio methods. The protocols allow to select the degree of approximation and computational demand such that they are applicable for realistic systems and still allow to control the quality of the approach. We demonstrate the capabilities of the different protocols using the CO dimer as a first example. Correlation effects are found to scale J by a factor of about 0.7 which is in good agreement to earlier results obtained for the ethene dimer. The various levels of the protocol allow to assess the influence of ionic configurations and the polarisation within the dimer. Further, the interplay between the Forster and Dexter contribution to J is investigated. The computations also show error compensation within approximations that are widely used for extended systems as in particular the transition density cube method. (C) 2007 Elsevier B.V. All rights reserved.