Bond energy decomposition analysis for subsystem density functional theory

We employed an explicit expression for the dispersion (D) energy in conjunction with Kohn-Sham (KS) density functional theory and frozen-density embedding (FDE) to calculate interaction energies between DNA base pairs and a selected set of amino acid pairs in the hydrophobic core of a small protein Rubredoxin. We use this data to assess the accuracy of an FDE-D approach for the calculation of intermolecular interactions. To better analyze the calculated interaction energies we furthermore propose a new energy decomposition scheme that is similar to the well-known KS bond formation analysis [F. M. Bickelhaupt and E. J. Baerends, Rev. Comput. Chem. 15, 1 (2000)10.1002/9780470125922.ch1], but differs in the electron densities used to define the bond energy. The individual subsystem electron densities of the FDE approach sum to the total electron density which makes it possible to define bond energies in terms of promotion energies and an explicit interaction energy. We show that for the systems considered only a few freeze-and-thaw cycles suffice to reach convergence in these individual bond energy components, illustrating the potential of FDE-D as an efficient method to calculate intermolecular interactions. © 2013 American Institute of Physics