Robust, basis-set independent method for the evaluation of charge-transfer energy in noncovalent complexes.

Separation of the energetic contribution of charge transfer to interaction energy in noncovalent complexes would provide important insight into the mechanisms of the interaction. However, the calculation of charge-transfer energy is not an easy task. It is not a physically well-defined term, and the results might depend on how it is described in practice. Commonly, the charge transfer is defined in terms of molecular orbitals; in this framework, however, the charge transfer vanishes as the basis set size increases toward the complete basis set limit. This can be avoided by defining the charge transfer in terms of the spatial extent of the electron densities of the interacting molecules, but the schemes used so far do not reflect the actual electronic structure of each particular system and thus are not reliable. We propose a spatial partitioning of the system, which is based on a charge transfer-free reference state, namely superimposition of electron densities of the noninteracting fragments. We show that this method, employing constrained DFT for the calculation of the charge-transfer energy, yields reliable results and is robust with respect to the strength of the charge transfer, the basis set size, and the DFT functional used. Because it is based on DFT, the method is applicable to rather large systems.